CN106881092B - A kind of preparation method of load type metal Raney nickel - Google Patents
A kind of preparation method of load type metal Raney nickel Download PDFInfo
- Publication number
- CN106881092B CN106881092B CN201710277325.8A CN201710277325A CN106881092B CN 106881092 B CN106881092 B CN 106881092B CN 201710277325 A CN201710277325 A CN 201710277325A CN 106881092 B CN106881092 B CN 106881092B
- Authority
- CN
- China
- Prior art keywords
- nickel
- nial
- scpiolitc
- load type
- type metal
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 239000007868 Raney catalyst Substances 0.000 title claims abstract description 36
- 229910000564 Raney nickel Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000002121 nanofiber Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 229910000943 NiAl Inorganic materials 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 24
- 238000006722 reduction reaction Methods 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 aluminum ions Chemical class 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 4
- 229940009827 aluminum acetate Drugs 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 29
- 230000007547 defect Effects 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 22
- 239000004113 Sepiolite Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 229910052624 sepiolite Inorganic materials 0.000 description 13
- 235000019355 sepiolite Nutrition 0.000 description 13
- 229910052596 spinel Inorganic materials 0.000 description 13
- 239000011029 spinel Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 210000003850 cellular structure Anatomy 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- LFYMLMKKOJHYFY-UHFFFAOYSA-N [O-2].[Al+3].[Ni+2] Chemical compound [O-2].[Al+3].[Ni+2] LFYMLMKKOJHYFY-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of load type metal Raney nickel of the present invention, is related to the catalyst comprising nickel, and this method is to prepare NiAl by one step of dipper precipitation method2O4/ scpiolitc nano-fiber composite material, then the composite material is restored in reducing atmosphere and obtains the NiAl of carried metal nickel2O4/ scpiolitc nano-fiber composite material, that is, load type metal Raney nickel, overcomes that existing load type metal Raney nickel preparation process is complicated, loaded article high temperature is easy to reunite, vector stabilisation is poor and defect at high cost.
Description
Technical field
Technical solution of the present invention is related to the catalyst comprising nickel, specifically a kind of load type metal Raney nickel
Preparation method.
Background technique
Noble metal catalyst such as Pt, Pd, Ru etc. have good catalytic activity and highly selective, but noble metal price is high
It is expensive, use is limited to a certain extent.Compared with noble metal, metallic nickel is due to resourceful, cheap and catalytic activity
High plurality of advantages is received significant attention and is applied in catalytic field.Metallic nickel is initially used to catalytic organism hydrogenation reaction,
Subsequent metallic nickel is widely used in as catalyst plus the processes such as hydrogen, coupling, oxidation and organic synthesis.The height of metallic catalyst
Temperature stability is poor, and suitable carrier helps to improve the stability and catalytic activity of catalyst, therefore answers in the industrial production
With it is more be load type metal Raney nickel, wherein the carrier of most widely used load type metal Raney nickel is Al2O3With
SiO2。
Since natural sepiolite race mineral have special cellular structure, there is great specific surface area, thus have good
Good adsorptivity, sepiolite mineral also have the excellent properties of catalytic, rheological characteristic and thermal stability, thus in industrial production
In usually use it as the carriers of the metal ions such as active component Zn, Cu, W, Fe, Ca, Ni.Document " Huang Mengguang, Zhou Jun, Peng Feng,
The structure and catalytic activity [J] Hunan University journal (from section's version) of equal .Ni- sepiolite catalyst, 1995,22 (4): 52-55. "
It is middle to introduce using sepiolite as carrier to load metal nickel, with tradition Al2O3Nickel-loaded is compared, it is active it is high, selectivity it is excellent and
The good advantage of stability, catalyst life are also obviously prolonged.But the research take single industrial scpiolitc as carrier into
Row load, high-temperature stability is poor, and the metallic nickel for being carried on industrial scpiolitc surface is easy in catalytic reaction process
The reaction such as high temperature sintering occurs, is substantially reduced its catalytic activity.
The preparation method of mineral loaded metal mainly has sol method, hydrothermal crystallizing reduction method, microemulsion infusion method and dipping
Reduction method etc..CN105879874A discloses the preparation method that a kind of coprecipitation prepares supported nickel catalyst, and this method is made
Tripolite loading Raney nickel specific surface area with higher and thermal stability.Such catalyst catalytic chemistry react when,
Surface metal catalyst is easily reunited in temperature elevation process, reduces the activity and catalytic effect of catalyst.
CN104923240A discloses a kind of preparation method of the nickel-base catalyst of sepiolite supported bimetallic-modified, and this method is dipping
Reduction method, obtained nickel-base catalyst have the defects that preparation cost is high, ageing-resistant ability is poor and service life is short.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of preparation method of load type metal Raney nickel, pass through
One step of dipper precipitation method prepares NiAl2O4/ scpiolitc nano-fiber composite material, then by the composite material in reproducibility gas
Reduction obtains nickel/NiAl in atmosphere2O4/ scpiolitc nano-fiber composite material, that is, carried metal nickel NiAl2O4/ sepiolite
The load type metal Raney nickel that mineral nano fibrous composite is constituted overcomes existing load type metal Raney nickel preparation
Complex process, loaded article high temperature is easy to reunite, vector stabilisation is poor and defect at high cost.
The present invention solves technical solution used by the technical problem: a kind of preparation side of load type metal Raney nickel
Method prepares NiAl by one step of dipper precipitation method2O4/ scpiolitc nano-fiber composite material, then by the composite material also
Reduction obtains nickel/NiAl in originality atmosphere2O4/ scpiolitc nano-fiber composite material, that is, carried metal nickel NiAl2O4/
The load type metal Raney nickel that scpiolitc nano-fiber composite material is constituted, the specific steps are as follows:
The first step prepares NiAl2O4/ scpiolitc nanofiber complex carrier:
NiAl is prepared using one step of dipper precipitation method2O4/ scpiolitc nanofiber complex carrier, steps are as follows:
The nickel metal salt and aluminum metal salt for weighing requirement are dissolved in deionized water, are configured to containing nickel ion and aluminum ions molten
Liquid is then added ethylene glycol, stirs 0.5~1.5h at 30~50 DEG C of constant temperature, scpiolitc nanofiber is then added, formed
Mixed liquor, wherein the molar ratio of nickel metal salt, aluminum metal salt and ethylene glycol is 1: 1~2: 10~15, total metal salt amount, Hai Pao
The mass ratio of stone ore object nanofiber amount and amount of deionized water is 1: 1.5~2.5: 10~20, then is added and rubs in aforesaid liquid
The precipitating reagent that your concentration is 0.002~0.003mol/mL, the pH value of control system stir 0.5 at 7~9,60~80 DEG C of constant temperature
~1.5h filters obtained suspension, and washing to pH is neutrality, obtained filter cake is placed in baking oven dry in 80~120 DEG C
It is dry, then dry solid abrasive is placed in Muffle furnace and is roasted in 400~800 DEG C, 6~8h is kept the temperature, then takes out laggard one
Step is ground to powdered, obtained NiAl2O4/ scpiolitc nanofiber complex carrier；
Second step prepares load type metal Raney nickel:
By NiAl made from the first step2O4/ scpiolitc nanofiber complex carrier is placed in atmosphere tube type furnace, is passed through
Reduction reaction gas keeps the temperature 3~9h at 450~750 DEG C, is made by nickel/NiAl2O4/ scpiolitc nanofiber composite wood
Material is the NiAl of carried metal nickel2O4The load type metal Raney nickel that/scpiolitc nano-fiber composite material is constituted.
A kind of preparation method of above-mentioned load type metal Raney nickel, the nickel metal salt are nickel nitrate, nickel sulfate or chlorine
Change nickel.
A kind of preparation method of above-mentioned load type metal Raney nickel, the aluminum metal salt are aluminum nitrate, aluminum acetate or chlorine
Change aluminium.
A kind of preparation method of above-mentioned load type metal Raney nickel, the precipitating reagent are ammonium carbonate, ammonium hydrogen carbonate or carbon
Sour sodium.
A kind of preparation method of above-mentioned load type metal Raney nickel, it is 5 that the reduction reaction gas, which is containing volume fraction,
Hydrogen nitrogen mixed gas, hydrogen sulfide gas or the ammonia of~10% hydrogen.
A kind of preparation method of above-mentioned load type metal Raney nickel, the scpiolitc nanofiber are pressed
CN200910070297.8 the method is made.
The preparation method of above-mentioned a kind of load type metal Raney nickel, except related scpiolitc nanofiber
Other raw materials, reagent and equipment pass through known approach and obtain, and operating procedure is that those skilled in the art will appreciate that.
Beneficial effects of the present invention are as follows:
Compared with prior art, the substantive distinguishing features outstanding that the present invention has are as follows:
(1) different carriers can make loaded catalyst have different property and catalytic performance.Natural sepiolite race mine
Object has complicated cellular structure, large specific surface area, therefore shows good adsorptivity and catalytic activity.And its price is low
It is honest and clean, it is free of a burden to environment, performance stablize, as catalyst carrier can improve product catalytic and stability again reduction at
This.But single natural sepiolite race mineral is taken to be loaded as carrier, high-temperature stability is poor, and is carried on mine
The metallic nickel on object surface is easy to happen the reaction such as high temperature sintering in catalytic reaction process, is substantially reduced its catalytic activity.
Spinel oxides are due to being located at the ion in tetrahedron gap and the ion of octahedral interstices in its crystal lattice
It can be replaced mutually, as a result lead to its property variability, have the characteristics that hardness is big, fusing point is high, chemical property is stable, while its
Thermal expansion coefficient is smaller, thus has good thermal stability and mechanical strength.Wherein Al system spinel is due to intracell Al3+
The difference of present position, thus there is different surface naturies.Specificity of the Al system spinel because of its surface nature, thermostabilization
The properties such as property, mechanical strength height receive extensive concern in catalytic field.
The present invention is by the spinel oxides NiAl with good catalytic activity2O4With scpiolitc nanofiber into
Row is compound, obtains a kind of composite carrier, effectively increases the catalytic activity and stability of carrier, and NiAl2O4In reaction process
In can be used as metal nickel source, extend the service life of catalyst.
(2) present invention has special structure and surface nature as the spinel oxides of loaded article, leads in catalysis
Domain application be even more receive significant attention and study, therefore spinel oxides preparation and structure regulating be research hot spot
One of.The preparation method of spinel oxides mainly has sol-gal process, solid reaction process and hydro-thermal method at present.Wherein colloidal sol
Gel method chemical uniformity is good, and product chemistry purity is high, product grain partial size is small, but hard aggregation easy to form after colloidal sol drying,
And it is raw materials used expensive, at high cost, volume contraction is big when dry, and yield is small, and it is longer the time required to sol-process, cause whole
Body long preparation period is only applicable to the laboratory applications high to product requirements, is subject to certain restrictions in industrial application.Solid phase is closed
It is formed at method using high-temperature calcination after metal oxide mixing, but the mixed process of reactant is that solid directly mixes, there are micro-
Not uniform enough the shortcomings that being not enough is mixed in sight, therefore its process is more complicated and uncontrollable, and due to solid phase
Intermediate ion diffusion velocity is slow, therefore needs long-time heating at high temperature, and energy consumption of reaction is high.Hydro-thermal method can be such that product does not need
Crystalline state, but at high cost, the selection and preparation of presoma with high purity of the raw material of hydro-thermal method requirement are directly becoming by high-temperature calcination
It is affected to reaction result, reaction process is difficult to control, and is needed in reaction using autoclave, technique is more complex.
Spinel oxide made from above-mentioned conventional preparation techniques is reunited seriously, and specific surface area is small, uses as catalyst
The defects of poor there are stability, needs to select suitable carrier progress compound, to improve the steady of product to overcome drawbacks described above
Qualitative, the present invention uses nickel aluminate type oxide NiAl2O4It is compound with the progress of scpiolitc nano fibre carrier, completely
Overcome drawbacks described above.
(3) present invention prepares NiAl using one step of dipper precipitation method2O4/ scpiolitc nanofiber complex carrier.Dipping
Reduction method be oxide is generated under the conditions of high-temperature calcination after metal salt solution is impregnated in scpiolitc nanofiber, then
It is restored in hydrogen atmosphere high temperature, has just been prepared into metal/scpiolitc nano-fiber catalyst.Coprecipitation preparation point is brilliant
Stone-type oxide is that precipitating reagent is added in one kind in salting liquid, after cationic precipitating completely, is obtained through filtering, drying, sintering
The method of metal composite oxide.The present invention combines the two, prepares nickel aluminate type oxygen using one step of dipper precipitation method
The advantages of compound/scpiolitc nano-fiber composite material, the method, is that content of metal is big, particle is small, is evenly distributed, and is urged
Agent activity is higher.
(4) prior art CN105879874A selects diatomite as catalyst carrier, and NiAl is used in the present invention2O4/
Scpiolitc nano-fiber composite material is as catalyst carrier.Compared with the carrier that CN105879874A is selected, sepiolite
There are a large amount of cellular structures in mineral nano fiber, and loaded article can be made in carrier surface and internal sufficiently load, improve load capacity；
NiAl2O4As a part of complex carrier, it can effectively improve carrier catalysis activity, improve the distributing homogeneity of metallic nickel, and
Nickel source is provided for subsequent catalyst reaction, extends catalyst service life.Prior art CN104923240A is to improve catalyst
Catalytic effect selects bimetallic to carry out with metallic nickel composite modified, and metal is unevenly distributed on sepiolite surface, high temperature easy-sintering group
It is poly-, make catalyst inactivation, service life is limited, and sepiolite is as sole support, poor high temperature stability.And the present invention by
Compound NiAl in scpiolitc nanofiber2O4Carrier also can be improved while improving catalyst activity as carrier
Stability, while as the metallic nickel of loaded article from NiAl2O4Middle reduction generates, and is evenly distributed in oxide surface, high-temperature stable
Property is good.
Compared with prior art, the present invention has following marked improvement:
(1) the method for the present invention reprocesses oxide on the basis of mineral fibres loads spinel oxides,
Prepare the compound support materials of carried metal.This method uses one step of dipper precipitation method to prepare composite material first.It is existing
Mode of loading need to process loaded article and carrier respectively, then the two is subjected to compound, complex steps, complex technical process.This
Invention contains the advantages that hydrophilic nmature and good dispersiveness of abundant hydroxyl using scpiolitc nanofiber, is added into gold
Belong to constant temperature stirring in salting liquid, in duct of the metal cation well into sepiolite fibre or is carried on after fiber surface again
Excessive precipitating reagent heating stirring is added, makes that metal cation precipitate completely and energy payload is in sepiolite fibre surface and duct
Inside finally obtains nickel aluminate type oxide/scpiolitc nano-fiber composite material by roasting.The method of the present invention
The preparation of spinel oxides is combined with the load of mineral fibres, simple process is easily operated.Secondly, side of the present invention
Method reprocesses above-mentioned composite material, and low temperature is restored under reduction reaction gas condition, makes metallic nickel from nickel aluminium point
Composite surface is reverted in spar oxide.Spinel oxides have certain catalytic activity, both can be used as load
Object can be used as catalyst carrier use again, improve catalyst stability.The present invention is first using spinel oxides as load
Object and the progress of scpiolitc nanofiber are compound, the catalytic activity of carrier are improved while guaranteeing vector stabilisation, again
Metallic nickel is restored from nickel aluminum oxide as carrier and is carried on oxide, and the presence of surface metal nickel, which is used as, urges
The active component of agent, due to surface metal nickel load in the surface of spinel oxides again overall load in scpiolitc
Nanofiber surface and inside, therefore surface is not susceptible to reunite as the metallic nickel of catalyst activity component in catalytic process
Equal side reactions, can effectively improve the catalytic performance of composite material.In addition, while catalytic reduction reaction carries out, carrier
In the surface of nickel aluminium composite oxide can increasingly generate the transiting metal nickel of part, urging for catalyst can be further improved
Change effect, extends catalyst service life.
(2) simple process of the method for the present invention is reasonable, and raw materials used and reagent is commercially available technical grade chemicals, and price is low
It is honest and clean, non-environmental-pollution.
(3) functional inexpensive nanocomposite can also be prepared using this method, has widened nickel aluminate
Type oxide/scpiolitc nano-fiber composite material application prospect.
Specific embodiment
Embodiment 1
The first step prepares NiAl2O4/ scpiolitc nanofiber complex carrier:
NiAl is prepared using one step of dipper precipitation method2O4/ scpiolitc nanofiber complex carrier, steps are as follows:
The nickel nitrate and nitric acid aluminium salt for weighing requirement are dissolved in deionized water, are configured to containing nickel ion and aluminum ions molten
Liquid is then added ethylene glycol, stirs 0.5h at 30 DEG C of constant temperature, and scpiolitc nanofiber is then added, and forms mixed liquor,
In, the molar ratio of nickel nitrate, aluminum nitrate and ethylene glycol is 1: 1: 10, total metal salt amount, scpiolitc nanofiber amount and is gone
The mass ratio of ion water is 1: 1.5: 10, then the precipitating reagent carbon that molar concentration is 0.002mol/mL is added in aforesaid liquid
The pH value of sour ammonium, control system stirs 0.5h at 7,60 DEG C of constant temperature, and obtained suspension is filtered, and washing to pH is neutrality,
Obtained filter cake is placed in baking oven in 80 DEG C of dryings, then dry solid abrasive is placed in Muffle furnace and is roasted in 400 DEG C,
6h is kept the temperature, powdered, obtained NiAl is further ground to after then taking out2O4/ scpiolitc nanofiber complex carrier；
Second step prepares load type metal Raney nickel:
By NiAl made from the first step2O4/ scpiolitc nanofiber complex carrier is placed in atmosphere tube type furnace, is passed through
Be reduction reaction gas containing the hydrogen nitrogen mixed gas that volume fraction is 5% hydrogen, keep the temperature 9h at 450 DEG C, be made by nickel/
NiAl2O4/ scpiolitc nano-fiber composite material, that is, carried metal nickel NiAl2O4/ scpiolitc nanofiber is compound
The load type metal Raney nickel that material is constituted.
Embodiment 2
The first step prepares NiAl2O4/ scpiolitc nanofiber complex carrier:
NiAl is prepared using one step of dipper precipitation method2O4/ scpiolitc nanofiber complex carrier, steps are as follows:
The nickel sulfate and aluminum acetate for weighing requirement are dissolved in deionized water, are configured to containing nickel ion and aluminum ions solution,
Ethylene glycol is then added, stirs 1h at 40 DEG C of constant temperature, scpiolitc nanofiber is then added, forms mixed liquor, wherein sulphur
The molar ratio of sour nickel, aluminum acetate and ethylene glycol is 1: 1.5: 12, total metal salt amount, scpiolitc nanofiber amount and deionization
The mass ratio of water is 1: 2: 15, then the precipitating reagent bicarbonate that molar concentration is 0.0025mol/mL is added in aforesaid liquid
The pH value of ammonium, control system stirs 1h at 8,70 DEG C of constant temperature, and obtained suspension is filtered, and washing to pH is neutrality, will
To filter cake be placed in baking oven in 100 DEG C of dryings, then by dry solid abrasive be placed in Muffle furnace in 600 DEG C roast, protect
Warm 7h is further ground to powdered, obtained NiAl after then taking out2O4/ scpiolitc nanofiber complex carrier；
Second step prepares load type metal Raney nickel:
By NiAl made from the first step2O4/ scpiolitc nanofiber complex carrier is placed in atmosphere tube type furnace, is passed through
Be reduction reaction gas containing the hydrogen nitrogen mixed gas that volume fraction is 6% hydrogen, keep the temperature 6h at 600 DEG C, be made by nickel/
NiAl2O4/ scpiolitc nano-fiber composite material, that is, carried metal nickel NiAl2O4/ scpiolitc nanofiber is compound
The load type metal Raney nickel that material is constituted.
Embodiment 3
The first step prepares NiAl2O4/ scpiolitc nanofiber complex carrier:
NiAl is prepared using one step of dipper precipitation method2O4/ scpiolitc nanofiber complex carrier, steps are as follows:
The nickel chloride and aluminium chloride for weighing requirement are dissolved in deionized water, are configured to containing nickel ion and aluminum ions solution,
Ethylene glycol is then added, stirs 1.5h at 50 DEG C of constant temperature, scpiolitc nanofiber is then added, forms mixed liquor, wherein
The molar ratio of nickel chloride, aluminium chloride and ethylene glycol is 1: 2: 15, total metal salt amount, scpiolitc nanofiber amount and deionization
The mass ratio of water is 1: 2.5: 20, then the precipitating reagent sodium carbonate that molar concentration is 0.003mol/mL is added in aforesaid liquid,
The pH value of control system stirs 1.5h at 9,80 DEG C of constant temperature, and obtained suspension is filtered, and washing to pH is neutrality, will obtain
Filter cake be placed in baking oven in 120 DEG C of dryings, then by dry solid abrasive be placed in Muffle furnace in 800 DEG C roast, heat preservation
8h is further ground to powdered, obtained NiAl after then taking out2O4/ scpiolitc nanofiber complex carrier；
Second step prepares load type metal Raney nickel:
By NiAl made from the first step2O4/ scpiolitc nanofiber complex carrier is placed in atmosphere tube type furnace, is passed through
Be reduction reaction gas containing the hydrogen nitrogen mixed gas that volume fraction is 10% hydrogen, keep the temperature 3h at 750 DEG C, be made by nickel/
NiAl2O4/ scpiolitc nano-fiber composite material, that is, carried metal nickel NiAl2O4/ scpiolitc nanofiber is compound
The load type metal Raney nickel that material is constituted.
Embodiment 4
In addition to reduction reaction gas used is hydrogen sulfide gas, other are the same as embodiment 1.
Embodiment 5
In addition to reduction reaction gas used is ammonia, other are the same as embodiment 2.
In above-described embodiment, the scpiolitc nanofiber is made by CN200910070297.8 the method, sea
Other raw materials, reagent and equipment except afrodite mineral nano fiber pass through known approach and obtain, and operating procedure is this field
What technical staff will appreciate that.
Claims (5)
1. a kind of preparation method of load type metal Raney nickel, it is characterised in that: prepared by one step of dipper precipitation method
NiAl2O4/ scpiolitc nano-fiber composite material, then the composite material restored in reducing atmosphere obtain nickel/
NiAl2O4/ scpiolitc nano-fiber composite material, that is, carried metal nickel NiAl2O4/ scpiolitc nanofiber is compound
The load type metal Raney nickel that material is constituted, the specific steps are as follows:
The first step prepares NiAl2O4/ scpiolitc nanofiber complex carrier:
NiAl is prepared using one step of dipper precipitation method2O4/ scpiolitc nanofiber complex carrier, steps are as follows:
The nickel metal salt and aluminum metal salt for weighing requirement are dissolved in deionized water, are configured to nickeliferous and aluminum ions solution, then
Ethylene glycol is added, stirs 0.5~1.5h at 30~50 DEG C of constant temperature, scpiolitc nanofiber is then added, form mixed liquor,
Wherein, the molar ratio of nickel metal salt, aluminum metal salt and ethylene glycol is 1: 1~2: 10~15, and total metal salt amount, scpiolitc are received
The mass ratio of rice fibre weight and amount of deionized water is 1: 1.5~2.5: 10~20, then molar concentration is added in aforesaid liquid and is
The precipitating reagent of 0.002~0.003mol/mL, the pH value of control system stir 0.5~1.5h at 7~9,60~80 DEG C of constant temperature,
Obtained suspension is filtered, washing to pH is neutrality, obtained filter cake is placed in baking oven in 80~120 DEG C of dryings, then will
Dry solid abrasive is placed in Muffle furnace to be roasted in 400~800 DEG C, is kept the temperature 6~8h, is further ground to after then taking out
It is powdered, NiAl is made2O4/ scpiolitc nanofiber complex carrier；
Second step prepares load type metal Raney nickel:
By NiAl made from the first step2O4/ scpiolitc nanofiber complex carrier is placed in atmosphere tube type furnace, is passed through reduction
Reaction gas keeps the temperature 3~9h at 450~750 DEG C, is made by nickel/NiAl2O4/ scpiolitc nano-fiber composite material is
The NiAl of carried metal nickel2O4The load type metal Raney nickel that/scpiolitc nano-fiber composite material is constituted.
2. a kind of preparation method of load type metal Raney nickel according to claim 1, it is characterised in that: the nickel metal
Salt is nickel nitrate, nickel sulfate or nickel chloride.
3. a kind of preparation method of load type metal Raney nickel according to claim 1, it is characterised in that: the aluminum metal
Salt is aluminum nitrate, aluminum acetate or aluminium chloride.
4. a kind of preparation method of load type metal Raney nickel according to claim 1, it is characterised in that: the precipitating reagent
For ammonium carbonate, ammonium hydrogen carbonate or sodium carbonate.
5. a kind of preparation method of load type metal Raney nickel according to claim 1, it is characterised in that: the reduction is anti-
Answering gas is the hydrogen nitrogen mixed gas, hydrogen sulfide gas or ammonia for being 5~10% hydrogen containing volume fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710277325.8A CN106881092B (en) | 2017-04-25 | 2017-04-25 | A kind of preparation method of load type metal Raney nickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710277325.8A CN106881092B (en) | 2017-04-25 | 2017-04-25 | A kind of preparation method of load type metal Raney nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106881092A CN106881092A (en) | 2017-06-23 |
| CN106881092B true CN106881092B (en) | 2019-03-05 |
Family
ID=59183027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710277325.8A Expired - Fee Related CN106881092B (en) | 2017-04-25 | 2017-04-25 | A kind of preparation method of load type metal Raney nickel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106881092B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321299A (en) * | 2017-08-30 | 2017-11-07 | 河北工业大学 | The preparation method of molybdenum disulfide and scpiolitc nanofiber composite adsorbing material |
| CN109569625B (en) * | 2018-12-24 | 2021-06-29 | 河北工业大学 | Method for preparing supported metal nickel-based catalyst |
| CN110479280B (en) * | 2019-07-17 | 2022-09-13 | 华南理工大学 | CO low-temperature selective methanation Ni-ZrO 2 /NiAl 2 O 4 Catalyst, preparation method and application thereof |
| CN114160131B (en) * | 2021-12-20 | 2023-11-24 | 河北工业大学 | Preparation method of freeze-dried modified sepiolite group mineral supported Pd monoatomic catalyst |
| CN114210313B (en) * | 2021-12-20 | 2023-12-05 | 河北工业大学 | Preparation method of high-dispersion sepiolite group mineral loaded Au monoatomic catalyst |
| CN114177904B (en) * | 2021-12-20 | 2023-11-24 | 河北工业大学 | Preparation method of Al-combined hydrothermal modified sepiolite group mineral supported Pt single-atom catalyst |
| CN114100608B (en) * | 2021-12-20 | 2023-11-28 | 河北工业大学 | Preparation method of heat modified sepiolite group mineral loaded Rh single-atom catalyst |
| CN114733530B (en) * | 2022-03-29 | 2023-11-03 | 陕西氢易能源科技有限公司 | Hydrogenation catalyst of organic liquid hydrogen storage carrier, and preparation method and application thereof |
| CN115532303B (en) * | 2022-08-09 | 2023-10-20 | 杭州三隆新材料有限公司 | Composite carrier hydrogenation catalyst and application thereof in catalytic color reduction of polytetramethylene ether glycol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107078A (en) * | 1994-07-07 | 1995-08-23 | 南开大学 | Catalyst used for carbon dioxide hydrogenation reaction |
| CN1121898A (en) * | 1995-06-20 | 1996-05-08 | 南开大学 | Methanation catalyst for purifying gas as raw material for synthesis of ammonia |
| CN101733104A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application |
| CN106512920A (en) * | 2015-09-15 | 2017-03-22 | 广西师范大学 | Preparation method for nickel-based meerschaum catalyst and catalytic-oxidation regeneration method for nickel-based meerschaum catalyst |
-
2017
- 2017-04-25 CN CN201710277325.8A patent/CN106881092B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107078A (en) * | 1994-07-07 | 1995-08-23 | 南开大学 | Catalyst used for carbon dioxide hydrogenation reaction |
| CN1121898A (en) * | 1995-06-20 | 1996-05-08 | 南开大学 | Methanation catalyst for purifying gas as raw material for synthesis of ammonia |
| CN101733104A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application |
| CN106512920A (en) * | 2015-09-15 | 2017-03-22 | 广西师范大学 | Preparation method for nickel-based meerschaum catalyst and catalytic-oxidation regeneration method for nickel-based meerschaum catalyst |
Non-Patent Citations (1)
| Title |
|---|
| In Situ Microstructural Control of Ni/Al2O3 and Ni/NiAl2O4 Composites from Layered Double Hydroxides;Eric D. Rodeghiero et al.,;《Chem. Mater.》;19971231;第9卷;第478-484页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106881092A (en) | 2017-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106881092B (en) | A kind of preparation method of load type metal Raney nickel | |
| CN106732647B (en) | A kind of perovskite type methyl hydride combustion catalyst and the preparation method and application thereof | |
| CN106925274B (en) | A kind of preparation method of load type metal Co catalysts | |
| CN105879876B (en) | The preparation method of nickel-base catalyst for methane and carbon dioxide preparing synthetic gas by reforming | |
| CN106824163B (en) | Composite oxides and preparation method thereof | |
| CN102275963B (en) | Preparation method of aluminium oxide material | |
| CN109395734B (en) | Preparation method of high-activity cobalt-based catalyst for propane low-temperature catalytic combustion, product and application thereof | |
| CN106238066B (en) | A kind of spherical porous perovskite type catalyst La0.4Sr0.6Mn0.8Fe0.2O3And its preparation method and application | |
| Luo et al. | A facile approach for the preparation of biomorphic CuO–ZrO2 catalyst for catalytic combustion of methane | |
| CN104190414B (en) | A kind of sodium borohydride reduction that adopts prepares Pd/ α-Al 2o 3the preparation method of catalyst | |
| CN110124711B (en) | Preparation method and desulfurization application of few-layer carbon nitride loaded tungsten trioxide nanoparticle catalyst | |
| CN107511147A (en) | A kind of high stability catalyst for catalytic oxidation and preparation method | |
| CN102765742B (en) | Preparation method of cerium oxide microspheres | |
| CN110368967B (en) | Acetic acid hydrogenation catalyst, preparation method and application thereof | |
| CN109126845A (en) | Supported transition metal carbide catalyst and its one-step synthesis method method | |
| CN109331810A (en) | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN103372432A (en) | Preparation method of selective hydrogenation catalyst for alkyne and diene | |
| CN110368933A (en) | It is a kind of using Ce-Ti composite oxides as ruthenium-based ammonia synthetic catalyst of carrier and preparation method thereof | |
| CN111151232A (en) | Preparation method of spherical alumina | |
| CN107460019B (en) | A kind of preparation method of nano-nickel oxide/nickel aluminate carrier of oxygen | |
| CN109718787A (en) | Cerium/yttrium stable Zirconia carrier and catalyst | |
| CN106430289B (en) | A kind of method of low temperature preparation high-specific area nano gallate spinel | |
| CN109277100A (en) | It is a kind of using cerium oxide as the ruthenium-based ammonia synthetic catalyst of carrier | |
| CN106994346B (en) | The preparation method of load type metal Co catalysts | |
| CN112169817B (en) | Perovskite type composite oxygen carrier and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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: 20190305 |