CN106000454A - Method for preparing metal@ zeolite single crystal capsule catalytic material without organic template - Google Patents
Method for preparing metal@ zeolite single crystal capsule catalytic material without organic template Download PDFInfo
- Publication number
- CN106000454A CN106000454A CN201610341082.5A CN201610341082A CN106000454A CN 106000454 A CN106000454 A CN 106000454A CN 201610341082 A CN201610341082 A CN 201610341082A CN 106000454 A CN106000454 A CN 106000454A
- Authority
- CN
- China
- Prior art keywords
- metal
- zeolite
- catalysis material
- water
- capsule
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 70
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000002775 capsule Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 112
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- 238000006555 catalytic reaction Methods 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000499 gel Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000009415 formwork Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000002082 metal nanoparticle Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 19
- 238000001914 filtration Methods 0.000 description 18
- 230000001112 coagulating effect Effects 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000003863 metallic catalyst Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- -1 hydrogen Sodium oxide Chemical class 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 2
- 229910001630 radium chloride Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LMABILRJNNFCPG-UHFFFAOYSA-L ethane-1,2-diamine;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].NCCN LMABILRJNNFCPG-UHFFFAOYSA-L 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to preparation of a metal catalyst, and aims to provide a method for preparing a metal@ zeolite single crystal capsule catalytic material without an organic template. The method for preparing the metal@ zeolite single crystal capsule catalytic material without the organic template comprises the following steps: loading a metal precursor onto a Beta zeolite crystal seed by an impregnation method, roasting the Beta zeolite crystal seed, fully stirring and mixing a roasted product with sodium hydroxide, an aluminum source, a silicon source and water to obtain a mixture, putting the mixture into a hydrothermal kettle for heating, taking out reaction products, and washing and drying the products to obtain the metal@ zeolite single crystal capsule catalytic material. According to the preparation method disclosed by the invention, a template reagent is definitely not used, so that the preparation method is very suitable for synthesizing a metal@ Beta and mercerized zeolite single crystal catalyst; furthermore, the raw materials used in a preparation process are lower in cost, and the preparation process is simple.
Description
Technical field
The present invention is about metallic catalyst preparation field, prepares metal@zeolite monocrystalline capsule particularly to without organic formwork
The method of catalysis material.
Background technology
Metallic catalyst is widely used in the field such as petrochemical industry, fine chemistry industry.At reaction conditions, metallic catalyst is past
Toward having higher activity, but it is because the reason such as heat stability, carbon distribution so that the life-span of catalyst is affected, and
Roasting is lived again and is often made metallic grow up during catalyst so that catalyst can not reach original activity.
In order to solve this problem, have developed metal@zeolite catalyst.This catalyst is by metal or metal-oxide
It is wrapped in zeolite crystal or polycrystalline.Because zeolite often has higher heat stability.So metallic catalyst is because amassing
Can be in high-temperature roasting to remove the unfavorable factors such as carbon distribution after the reason inactivations such as carbon, without catalyst is burnt out.
But, the method that major part synthesizes this catalyst is more complicated, and more can fill molecular sieve because employing
The template in duct, cause metal in the product obtained well not wrapped up by zeolite.Many synthetic methods are in order to incite somebody to action
Metal parcel is tight, and metal is made bigger granule, has then wrapped up the thickest zeolite layer, has caused in catalyst
Metal active can not well play.And some method is tight in order to be wrapped up by metal, use more stable metal complex
Thing is presoma, and these presomas are the most expensive, are unfavorable for large-scale industrial application.So synthesis metal@zeolite
Single crystalline catalyst need nonetheless remain for us and makes great efforts research.
Summary of the invention
Present invention is primarily targeted at and overcome deficiency of the prior art, it is provided that a kind of without template prepare metal@Beta with
The method of modenite monocrystalline capsule catalysis material.For solving above-mentioned technical problem, the solution of the present invention is:
Thering is provided the method preparing metal@zeolite monocrystalline capsule catalysis material without organic formwork, concrete grammar is as described below:
Take metal precursor and load on Beta zeolite seed crystal by infusion process, roasting 0.5～5h at 100～500 DEG C；
Product of roasting is thoroughly mixed with sodium hydroxide, aluminum source, silicon source and water, and loads in water heating kettle, 100～
After heating 48～240 hours at 180 DEG C, product is taken out and carries out washing, being dried, i.e. prepare metal@zeolite list
Zeolite in brilliant capsule catalysis material, and metal@zeolite monocrystalline capsule catalysis material is Beta and mercerising (MOR) boiling
Any one in stone；
Wherein, the crystal seed in product of roasting, sodium hydroxide, aluminum source, silicon source, the mol ratio of water be 0.01～2.5:0～
2.5:0～0.6:10:2.0～200.0 (the preferably crystal seed in product of roasting, sodium hydroxide, aluminum source, silicon source, water
Mol ratio is 0.01～1.0:0～2.5:0～crystal seed in 0.6:10:2.0～200.0, and product of roasting, hydroxide
Sodium, aluminum source, silicon source, water at most can only there is one be not added with)；
Source of aluminium is any one in sodium aluminate, aluminium oxide, Alumina gel, aluminum isopropylate.；
Described silicon source is arbitrary a kind of in nano silicon, thin silica gel, thick silica gel, Ludox, waterglass；
Described metal precursor refers to the nitrate of metal, chloride, ethylenediamine complex or any silica supported metal,
Metal is arbitrary a kind of in gold, silver, platinum, rhodium, palladium, ferrum, cobalt or nickel.
In the present invention, in described prepared metal@zeolite monocrystalline capsule catalysis material, the sial atomic ratio of zeolite is 5 to arrive
Positive infinity, the specific surface area of metal@zeolite monocrystalline capsule catalysis material is 300～800m2Between/g.
In the present invention, described prepared metal@zeolite monocrystalline capsule catalysis material, metal nanoparticle is packaged into
In Beta or modenite crystal, metal mass fraction in metal@zeolite monocrystalline capsule catalysis material 0.01～
Between 10%.
Compared with prior art, the invention has the beneficial effects as follows:
In the preparation method of the present invention, entirely without using template, it is especially suitable for synthesizing metal Beta and modenite
Single crystalline catalyst；It addition, the cost of material used in preparation process of the present invention is relatively low, preparation process is simple.
The metal@Beta of present invention synthesis and modenite monocrystalline capsule catalysis material, product yield is higher, and metal utilizes
Rate is higher, and particle diameter is less, has been provided simultaneously with high activity and high stability.And be catalyzed at gained metal@zeolite monocrystalline capsule
In material, metallic particles is well wrapped up by zeolite monocrystalline, and the content of metal is controlled, and mass fraction is 0.01～10%
In the range of adjustable.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail:
The following examples can make the professional and technical personnel of this specialty that the present invention be more fully understood, but never in any form
Limit the present invention.Wherein, ethylenediamine complex is bought from Sigma-Aldrich company.
Embodiment 1
0.03g diethylene triamine Auric chloride. is impregnated on 1gBeta zeolite seed crystal, and 100 DEG C are burnt 5 hours.0.75g sodium aluminate,
1.00g sodium hydroxide is dissolved in 36.00g water, adds the thin silica gel of 6.00g, stirs, add above-mentioned 0.61g crystal seed,
The gel mole of gained consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:2.5:0.6:10:
200, load in water heating kettle, place 2 days for 100 DEG C, sucking filtration, washing, be dried, obtain gold@Beta molecular sieve, wherein
The mass fraction of gold is 0.1%, and silica alumina ratio is 20, and specific surface area is 350m2/g。
Embodiment 2
0.20g gold chloride is impregnated on 0.8gBeta zeolite seed crystal, and 200 DEG C are burnt 4 hours.0.75g sodium aluminate, 0.80g hydrogen
Sodium oxide is dissolved in 27.00g water, adds the thin silica gel of 6.00g, stirs, and adds 0.3g crystal seed, and the gel of gained rubs
You consist of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:2.0:0.6:10:150, load
In water heating kettle, place 3 days for 100 DEG C, sucking filtration, washing, be dried, obtain gold@mercerising molecular sieve, the wherein quality of gold
Mark is 0.5%, and silica alumina ratio is 20, and specific surface area is 350m2/g。
Embodiment 3
0.50g silver nitrate is impregnated on 0.6gBeta zeolite seed crystal, and 500 DEG C are burnt 0.5 hour.0.12g aluminium oxide, 0.40g
Sodium hydroxide is dissolved in 10.00g water, adds the thick silica gel of 6.00g, stirs, and adds 0.30g crystal seed, coagulating of gained
Glue mole consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:1.0:0.3:10:100,
Load in water heating kettle, place 10 days for 180 DEG C, sucking filtration, washing, be dried, obtain silver@mercerising molecular sieve, wherein silver
Mass fraction is 2%, and silica alumina ratio is 50, and specific surface area is 550m2/g。
Embodiment 4
0.25g silver nitrate is impregnated on 0.6gBeta zeolite seed crystal, and 500 DEG C are burnt 0.5 hour.0.75g sodium aluminate, 0.40g
Sodium hydroxide is dissolved in 22.50g water, adds the thin silica gel of 6.00g, stirs, add above-mentioned 0.61g crystal seed, gained
Gel mole consist of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:1.0:0.6:10:125,
Load in water heating kettle, place 3 days for 100 DEG C, sucking filtration, washing, be dried, obtain silver@Beta molecular sieve, wherein silver
Mass fraction is 1%, and silica alumina ratio is 20, and specific surface area is 350m2/g。
Embodiment 5
0.2g chloroplatinic acid is impregnated on 0.3gBeta zeolite seed crystal, and 300 DEG C are burnt 4 hours.0.12g aluminum isopropylate., 0.40g
Sodium hydroxide is dissolved in 8.00g water, adds the thick silica gel of 6.00g, stirs, and adds 0.15g crystal seed, coagulating of gained
Glue mole consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.25:1.0:0.15:10:50,
Load in water heating kettle, place 3 days for 180 DEG C, sucking filtration, washing, be dried, obtain platinum@mercerising molecular sieve, wherein platinum
Mass fraction is 0.4%, and silica alumina ratio is 100, and specific surface area is 800m2/g。
Embodiment 6
0.05g ethylenediamine platinum chloride is impregnated on 0.1gBeta zeolite seed crystal, and 400 DEG C are burnt 2 hours.0.06g aluminum isopropylate.,
0.40g sodium hydroxide is dissolved in 8.00g water, adds the thick silica gel of 6.00g, stirs, and adds 0.06g crystal seed, gained
Gel mole consist of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.1:1.0:0.08:10:
100, load in water heating kettle, place 3 days for 180 DEG C, sucking filtration, washing, be dried, obtain platinum@Beta molecular sieve, wherein
The mass fraction of platinum is 0.15%, and silica alumina ratio is 200, and specific surface area is 800m2/g。
Embodiment 7
0.60g radium chloride is impregnated on 0.6gBeta zeolite seed crystal, and 300 DEG C are burnt 4 hours.0.30g Alumina gel, 0.20g hydrogen
Sodium oxide is dissolved in 13.00g water, adds 6.00g nano silicon, stirs, and adds 0.62g crystal seed, gained
Gel mole consist of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:0.5:0.15:10:100,
Load in water heating kettle, place 3 days for 140 DEG C, sucking filtration, washing, be dried, obtain rhodium@Beta molecular sieve, wherein rhodium
Mass fraction is 2%, and silica alumina ratio is 100, and specific surface area is 300m2/g。
Embodiment 8
0.5g Palladous chloride. is impregnated on 0.6gBeta zeolite seed crystal, and 400 DEG C are burnt 1 hour.0.04g sodium hydroxide is dissolved in 0.36g
In water, add 20.00g Ludox, stir, add 0.3g crystal seed, the gel mole of gained consist of crystal seed,
Sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:0.1:0:10:2, load in water heating kettle, 100 DEG C of placements
3 days, sucking filtration, washing, it is dried, obtains palladium@mercerising molecular sieve, wherein the mass fraction of palladium is 3%, and silica alumina ratio is nothing
Poor big, specific surface area is 550m2/g。
Embodiment 9
0.60g Palladous nitrate. is impregnated on 0.6gBeta zeolite seed crystal, and 200 DEG C are burnt 2 hours.0.04g sodium hydroxide is dissolved in 4.00g
In water, add 20.00g Ludox, stir, add 0.6g crystal seed, the gel mole of gained consist of crystal seed,
Sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:0.1:0:10:20, load in water heating kettle, 100 DEG C of placements
3 days, sucking filtration, washing, it is dried, obtains palladium@mercerising molecular sieve, wherein the mass fraction of palladium is 3%, and silica alumina ratio is nothing
Poor big, specific surface area is 650m2/g。
Embodiment 10
0.8g ethylenediamine Palladous chloride. is impregnated on 0.6gBeta zeolite seed crystal, and 400 DEG C are burnt 0.5 hour.0.04g sodium hydroxide
It is dissolved in 8.00g water, adds 20.00g Ludox, stir, add 0.6g crystal seed, the gel mole composition of gained
It is 1:0.1:0:10:40 for crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water, loads in water heating kettle, 100 DEG C
Placing 3 days, sucking filtration, washing, be dried, obtain palladium@Beta molecular sieve, wherein the mass fraction of palladium is 3%, sial
Than for infinitely great, specific surface area is 550m2/g。
Embodiment 11
0.3g iron chloride is impregnated on 0.6gBeta zeolite seed crystal, and 300 DEG C are burnt 5 hours.0.06g aluminum isopropylate. is dissolved in 6.00g
In water, add 18.00g waterglass, stir, add 0.06g crystal seed, the gel mole of gained consist of crystal seed,
Sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.01:0:0.6:10:30, load in water heating kettle, 120 DEG C
Place 3 days, sucking filtration, washing, be dried, obtain ferrum@mercerising molecular sieve, the wherein mass fraction 0.1% of ferrum, silica alumina ratio
Being 200, specific surface area is 450m2/g。
Embodiment 12
1.8g ferric nitrate is impregnated on 0.6gBeta zeolite seed crystal, and 300 DEG C are burnt 4 hours.0.06g aluminum isopropylate. is dissolved in 6.00g
In water, add 18.00g waterglass, stir, add 0.66g crystal seed, the gel mole of gained consist of crystal seed,
Sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:0:0.6:10:30, load in water heating kettle, 120 DEG C of placements
3 days, sucking filtration, washing, it is dried, obtains ferrum@Beta molecular sieve, the wherein mass fraction 3% of ferrum, silica alumina ratio is 200,
Specific surface area is 450m2/g。
Embodiment 13
2.0g cobalt nitrate is impregnated on 0.6gBeta zeolite seed crystal, and 400 DEG C are burnt 2 hours.0.06g aluminum isopropylate., 0.08g
Sodium hydroxide is dissolved in 6.00g water, adds 18.00g waterglass, stirs, and adds 0.67g crystal seed, coagulating of gained
Glue mole consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:0.2:0.6:10:30, loads
In water heating kettle, place 3 days for 120 DEG C, sucking filtration, washing, be dried, obtain cobalt@mercerising molecular sieve, the wherein quality of cobalt
Mark 7%, silica alumina ratio is 200, and specific surface area is 450m2/g。
Embodiment 14
2.2g cobaltous chloride is impregnated on 0.6gBeta zeolite seed crystal, and 400 DEG C are burnt 2 hours.0.06g aluminum isopropylate., 0.08g
Sodium hydroxide is dissolved in 6.00g water, adds 18.00g waterglass, stirs, and adds 0.68g crystal seed, coagulating of gained
Glue mole consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:0.2:0.6:10:30, dress
Enter in water heating kettle, place 3 days for 200 DEG C, sucking filtration, washing, be dried, obtain cobalt@Beta molecular sieve, the wherein matter of cobalt
Amount mark 4%, silica alumina ratio is 200, and specific surface area is 700m2/g。
Embodiment 15
2.2g nickel impregnation is on 0.6gBeta zeolite seed crystal, and 400 DEG C are burnt 2 hours.0.06g aluminum isopropylate., 0.08g
Sodium hydroxide is dissolved in 6.00g water, adds 18.00g waterglass, stirs, and adds 0.64g crystal seed, coagulating of gained
Glue mole consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:0.2:0.6:10:30, dress
Enter in water heating kettle, place 3 days for 120 DEG C, sucking filtration, washing, be dried, obtain nickel@mercerising molecular sieve, the wherein matter of nickel
Amount mark 10%, silica alumina ratio is 200, and specific surface area is 450m2/g。
Embodiment 16
1.5g Nickel dichloride. is impregnated into 0.6gBeta zeolite seed crystal, and 500 DEG C are burnt 0.5 hour.0.06g aluminum isopropylate., 0.08g
Sodium hydroxide is dissolved in 6.00g water, adds 18.00g waterglass, stirs, and adds 0.65g crystal seed, coagulating of gained
Glue mole consists of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:0.2:0.6:10:30),
Load in water heating kettle, place 3 days for 120 DEG C, sucking filtration, washing, be dried, obtain nickel@Beta molecular sieve, wherein nickel
Mass fraction 6%, silica alumina ratio is 200, and specific surface area is 450m2/g。
Embodiment 17
0.25g silver nitrate is impregnated on 0.3gBeta zeolite seed crystal, and 500 DEG C are burnt 0.5 hour.0.75g sodium aluminate, 0.40g
Sodium hydroxide is dissolved in 20.00g water, adds the thin silica gel of 6.00g, stirs, add above-mentioned 0.61g crystal seed, gained
Gel mole consist of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 0.5:1.0:0.6:10:100,
Load in water heating kettle, place 3 days for 120 DEG C, sucking filtration, washing, be dried, obtain silver@Beta molecular sieve, wherein silver
Mass fraction is 1%, and silica alumina ratio is 5, and specific surface area is 350m2/g。
Embodiment 18
0.60g radium chloride is impregnated on 0.6gBeta zeolite seed crystal, and 300 DEG C are burnt 4 hours.0.30g Alumina gel, 0.20g hydrogen
Sodium oxide is dissolved in 13.00g water, adds 6.00g 5% rhodium/silicon dioxide, stirs, and adds 0.62g crystal seed, institute
Gel mole consist of crystal seed, sodium hydroxide, aluminum source, silicon source, the mol ratio of water are 1:0.5:0.15:10:
100, load in water heating kettle, place 3 days for 140 DEG C, sucking filtration, washing, be dried, obtain rhodium@Beta molecular sieve, wherein
The mass fraction of rhodium is 4%, and silica alumina ratio is 100, and specific surface area is 300m2/g。
It is only the specific embodiment of the present invention finally it should be noted that listed above.It is clear that the invention is not restricted to
Above example, it is also possible to have many variations.Those of ordinary skill in the art can from present disclosure directly
The all deformation derived or associate, are all considered as protection scope of the present invention.
Claims (3)
1. the method preparing metal@zeolite monocrystalline capsule catalysis material without organic formwork, it is characterised in that concrete grammar
As described below:
Take metal precursor and load on Beta zeolite seed crystal by infusion process, roasting 0.5～5h at 100～500 DEG C；
Product of roasting is thoroughly mixed with sodium hydroxide, aluminum source, silicon source and water, and loads in water heating kettle, 100～
After heating 48～240 hours at 180 DEG C, product is taken out and carries out washing, being dried, i.e. prepare metal@zeolite list
Zeolite in brilliant capsule catalysis material, and metal@zeolite monocrystalline capsule catalysis material is any in Beta and modenite
A kind of；
Wherein, the crystal seed in product of roasting, sodium hydroxide, aluminum source, silicon source, the mol ratio of water be 0.01～2.5:0～
2.5:0～0.6:10:2.0～200.0；
Source of aluminium is any one in sodium aluminate, aluminium oxide, Alumina gel, aluminum isopropylate.；
Described silicon source is arbitrary a kind of in nano silicon, thin silica gel, thick silica gel, Ludox, waterglass；
Described metal precursor refers to the nitrate of metal, chloride, ethylenediamine complex or any silica supported metal,
Metal is arbitrary a kind of in gold, silver, platinum, rhodium, palladium, ferrum, cobalt or nickel.
The method preparing metal@zeolite monocrystalline capsule catalysis material without organic formwork the most according to claim 1,
It is characterized in that, in described prepared metal@zeolite monocrystalline capsule catalysis material the sial atomic ratio of zeolite be 5 to just without
Poor big, the specific surface area of metal@zeolite monocrystalline capsule catalysis material is 300～800m2Between/g.
The method preparing metal@zeolite monocrystalline capsule catalysis material without organic formwork the most according to claim 1,
It is characterized in that, described prepared metal@zeolite monocrystalline capsule catalysis material, metal nanoparticle is packaged into Beta
Or in modenite crystal, metal mass fraction in metal@zeolite monocrystalline capsule catalysis material 0.01～10% it
Between.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610341082.5A CN106000454B (en) | 2016-05-20 | 2016-05-20 | The method that no organic formwork prepares metal@zeolite monocrystalline capsule catalysis material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610341082.5A CN106000454B (en) | 2016-05-20 | 2016-05-20 | The method that no organic formwork prepares metal@zeolite monocrystalline capsule catalysis material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106000454A true CN106000454A (en) | 2016-10-12 |
| CN106000454B CN106000454B (en) | 2019-01-08 |
Family
ID=57095826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610341082.5A Active CN106000454B (en) | 2016-05-20 | 2016-05-20 | The method that no organic formwork prepares metal@zeolite monocrystalline capsule catalysis material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106000454B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097302A (en) * | 2017-12-15 | 2018-06-01 | 广州华园科技有限公司 | A kind of hollow type high dispersive Fe@Beta molecular sieve catalysts and its preparation method and application |
| CN109569712A (en) * | 2018-08-24 | 2019-04-05 | 南京大学 | One kind being used for CO2The catalyst and its preparation method and purposes of hydrogenating reduction production ethyl alcohol |
| CN109701614A (en) * | 2018-12-24 | 2019-05-03 | 大连理工大学 | A kind of preparation method of hud typed Beta molecular sieve catalyst |
| CN112570015A (en) * | 2020-12-22 | 2021-03-30 | 天津大学 | Molecular sieve catalyst for packaging Pd-based alloy and preparation method and application thereof |
| CN112844456A (en) * | 2021-01-21 | 2021-05-28 | 中国工程物理研究院核物理与化学研究所 | Preparation method and application of core-shell type metal zeolite catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249968A (en) * | 2008-03-10 | 2008-08-27 | 吉林大学 | Method for synthesizing Beta molecular sieve by organic-free template |
| CN102285667A (en) * | 2011-06-09 | 2011-12-21 | 浙江大学 | Method for efficiently synthesizing beta molecular sieve without using organic template |
| WO2014086300A1 (en) * | 2012-12-09 | 2014-06-12 | Basf Se | Organotemplate-free solid-state synthetic method for zeolite molecular sieves |
-
2016
- 2016-05-20 CN CN201610341082.5A patent/CN106000454B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249968A (en) * | 2008-03-10 | 2008-08-27 | 吉林大学 | Method for synthesizing Beta molecular sieve by organic-free template |
| CN102285667A (en) * | 2011-06-09 | 2011-12-21 | 浙江大学 | Method for efficiently synthesizing beta molecular sieve without using organic template |
| WO2014086300A1 (en) * | 2012-12-09 | 2014-06-12 | Basf Se | Organotemplate-free solid-state synthetic method for zeolite molecular sieves |
Non-Patent Citations (1)
| Title |
|---|
| HAIYAN ZHANG, ET AL: "One-pot synthesis of Fe-Beta zeolite by an organotemplate-free and seed-directed route", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097302A (en) * | 2017-12-15 | 2018-06-01 | 广州华园科技有限公司 | A kind of hollow type high dispersive Fe@Beta molecular sieve catalysts and its preparation method and application |
| CN108097302B (en) * | 2017-12-15 | 2020-06-05 | 广州华园科技有限公司 | Hollow high-dispersion Fe @ Beta molecular sieve catalyst and preparation method and application thereof |
| CN109569712A (en) * | 2018-08-24 | 2019-04-05 | 南京大学 | One kind being used for CO2The catalyst and its preparation method and purposes of hydrogenating reduction production ethyl alcohol |
| CN109569712B (en) * | 2018-08-24 | 2022-04-22 | 南京大学 | For CO2Catalyst for producing ethanol by hydrogenation reduction and preparation method and application thereof |
| CN109701614A (en) * | 2018-12-24 | 2019-05-03 | 大连理工大学 | A kind of preparation method of hud typed Beta molecular sieve catalyst |
| CN112570015A (en) * | 2020-12-22 | 2021-03-30 | 天津大学 | Molecular sieve catalyst for packaging Pd-based alloy and preparation method and application thereof |
| CN112570015B (en) * | 2020-12-22 | 2022-08-26 | 天津大学 | Molecular sieve catalyst for packaging Pd-based alloy and preparation method and application thereof |
| CN112844456A (en) * | 2021-01-21 | 2021-05-28 | 中国工程物理研究院核物理与化学研究所 | Preparation method and application of core-shell type metal zeolite catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106000454B (en) | 2019-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106000454A (en) | Method for preparing metal@ zeolite single crystal capsule catalytic material without organic template | |
| CN106000453A (en) | Method for preparing metal @ZSM-5 zeolite single crystal capsule catalytic material | |
| CN110270348B (en) | Noble metal monatomic catalyst and preparation and application thereof | |
| CN107285334B (en) | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve | |
| CN109092371B (en) | In-situ synthesis method of Pd-IL/mesoporous Al2O3Method for preparing catalyst and its application | |
| CN103803579B (en) | Core-shell structured ZSM-5 composite molecular sieve and preparation method thereof | |
| CN105237565B (en) | A kind of metal-organic framework materials and its application based on plumbi nitras | |
| CN107690420A (en) | Aluminosilicate zeolites SSZ 98 synthesis | |
| CN101250428A (en) | In-situ crystallization cracking catalyst and preparation method thereof | |
| WO2006020648A9 (en) | Fluid/slurry bed cobalt-alumina catalyst made by compounding and spray drying | |
| CN108080022B (en) | Catalyst for preparing gasoline by naphtha coupled methanol and preparation method thereof | |
| CN107848820A (en) | The method for preparing zeolite SSZ 98 | |
| CN105597743A (en) | Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate | |
| CN106000449B (en) | The method that solid phase prepares metal@zeolite monocrystalline capsule catalysis material | |
| CN108654596A (en) | A kind of propane dehydrogenation catalyst and preparation method thereof | |
| CN113181926B (en) | Ammonia synthesis catalyst of cerium oxide loaded high surface defect cobalt oxide | |
| CN108160105B (en) | Molecular sieve catalyst for methane selective catalytic reduction and synthesis method thereof | |
| CN103803580B (en) | Isomorphous ZSM-5 composite molecular screen of a kind of nucleocapsid structure and preparation method thereof | |
| CN111054326A (en) | Supported catalyst, preparation method thereof and application of supported catalyst in catalyzing synthesis of indole from ethylene glycol and aniline | |
| CN109908947A (en) | A kind of highly selective catalyst for converting acetic acid processed of synthesis gas and its application | |
| CN109569653A (en) | It is a kind of for synthesizing the preparation method and application of the catalyst of amine terminated polyether | |
| JPS59170019A (en) | Manufacture of hydrocarbon mixture | |
| NL2024660B1 (en) | Sepiolite derived catalyst with spinel structure, and preparation method and application thereof | |
| CN105642318B (en) | The preparation method of catalyst of catalytic oxidation of hydrogen chloride for preparing chlorine gas and application | |
| CN103313792A (en) | Method of making and using hydrocarbon conversion catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |