CN109433209A - Nickel-boron amorphous alloy catalyst and its preparation method and application - Google Patents
Nickel-boron amorphous alloy catalyst and its preparation method and application Download PDFInfo
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- CN109433209A CN109433209A CN201811121120.1A CN201811121120A CN109433209A CN 109433209 A CN109433209 A CN 109433209A CN 201811121120 A CN201811121120 A CN 201811121120A CN 109433209 A CN109433209 A CN 109433209A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 40
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 34
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 230000000536 complexating effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 14
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 abstract description 7
- 238000007772 electroless plating Methods 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 6
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Abstract
The present invention discloses a kind of nickel-boron amorphous alloy catalyst and preparation method thereof, belongs to chemical field；This method uses sol-gel method joint electroless plating method to prepare nickel-boron amorphous alloy catalyst n i-B/TiO for the first time2‑ZrO2, hydrogenated rosin is prepared for catalytic hydrogenation of rosin；Reaction condition of the present invention is mild, energy saving, and specific surface area of catalyst is high, and dosage is few, abietic type acid's high conversion rate, and tetrahydroabietic acid selectivity is high.
Description
Technical field
The present invention relates to a kind of nickel-boron amorphous alloy catalyst and its preparation method and application, belong to chemical field.
Background technique
Rosin is to be secreted by pine tree or extracted by solvent impregnated pine tree fragment, then the one kind obtained through distilation is naturally set
Rouge.In China, pine forest area accounts for about global 1/3, and rosin is resourceful, and the neck such as be widely used in chemical industry, papermaking, coating
Domain.Rosin is carried out plus hydrogen, disproportionation, isomerization etc. are modified, can improve easily be oxidized, the disadvantages such as softening point is low.Hydrogenated rosin is
Rosin carries out the product that hydrogenation reaction obtains under the action of catalyst, it has, and good in oxidation resistance, thermal stability are high, brittleness is small,
The advantages that of light color, is widely used in the industry such as adhesive, scaling powder, rubber, coating and printing ink, papermaking.Rosin adds hydrogen universal at present
Using precious metals pd/C catalyst, but because its is at high cost, specific surface area is small, easily fire the disadvantages of so that base metal Cu, Ni,
The crystalline-state catalysts such as Raney nickel part is hydrogenated instead of precious metal catalyst rosin, but catalytic activity is lower than noble metal catalyst；Separately
There is researcher to report using the research of the ni based amorphous alloy catalyst such as Ni-B, Ni-P outside, and can achieve Pd/C catalysis
The disadvantages of equivalent effect of agent substantially reduces catalyst cost, but uneven, easy to reunite there are Active components distribution.
Summary of the invention
It is an object of that present invention to provide a kind of preparation methods of nickel-boron amorphous alloy catalyst, using the catalyst
Rosin hydrogenation reaction has process flow simple, and reaction pressure is lower, and energy saving, catalyst amount is few, abietic acid conversion ratio
The characteristics of height, good product quality.
Present invention employs electroless plating method joint sol-gel methods to prepare carried non-crystal Ni-B catalyst, reduces
Catalyst cost exposes more active sites, Active sites density with higher compared to crystalline-state catalyst；Phase
Than overcoming the disadvantages of Active components distribution is uneven, easy to reunite in the Ni-B catalyst of non-loading type, while improving catalyst
Thermal stability, catalyst life obtained is long, provides a new way for rosin catalyzed plus hydrogen.
The method of the present invention specifically includes the following steps:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is 1:(0.3~1): the ratio of (1~5), by metatitanic acid fourth
Ester, zirconium oxychloride and dehydrated alcohol are added in three-necked flask, then in 40~60 DEG C of stirred in water bath to complete miscibility, adjust pH
Value is 2~4；
(2) Ti:H is pressed2The molar ratio of O be 1:(10~30) ratio, be slowly added to deionized water in step (1) mixture,
It is hydrolyzed into gel mixture, after still aging 24~48h, dry 12 at 60~100 DEG C~for 24 hours；
(3) mixture after drying is placed at 400~550 DEG C and roasts 2~4h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, be added ethylenediamine complexing, by Ni:B molar ratio be 1:(1~3) ratio, add
Enter KBH4Solution, it is 10~14 that NaOH solution, which adjusts pH value, and Ni-B plating solution is made, and wherein the molar ratio of nickel sulfate and ethylenediamine is
1:(3~9)；
(5) TiO is added in the plating solution2-ZrO2Complex carrier, 20~40min of microwave heating at 40~60 DEG C, in being washed to
Property, alcohol washes, and is dried in vacuo, and obtained black solid is nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2。
The NaOH solution concentration is 10 mol/L.
The TiO of 0.25~1.25g is added in the plating solution of every 100mL2-ZrO2Complex carrier.
Another object of the present invention is to provide nickel-boron amorphous alloy catalyst n i-B/TiO made from the above method2-ZrO2。
By nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2In rosin hydrogenation reaction, the specific steps are as follows:
(1) by nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2With the ratio of the rosin after melting in mass ratio 3~10%
It is added in autoclave, seals reaction kettle:
(2) N is used at 0.1~0.5MPa2By air displacement 3 times in reaction kettle, then use H23 are replaced at 0.1~0.5MPa
It is secondary, and check air-tightness；
(3) H is opened2Intake valve, adjusting reacting kettle inner pressure are 3~6MPa, are started to warm up, in 170~200 DEG C, revolving speed 500
2~5h is reacted under the conditions of~1000r/min, obtains hydrogenated rosin.
Used rosin is level-one, used H2For industrial hydrogen.
Compared with the existing technology, the present invention has the following advantages or good effect:
(1) Ni-B/TiO is prepared using electroless plating method joint sol-gel method2-ZrO2Catalyst is used for rosin hydrogenation reaction, produces
Abietic type acid's high conversion rate in object, tetrahydroabietic acid selectivity are high；
(2) process conditions are mild, and the specific surface area of catalyst prepared under this condition is high, and thermal stability is good；
(3) catalyst life is long, and reusable 9~10 times.
Specific embodiment
Below with reference to example, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1: the preparation method and application of this nickel-boron amorphous alloy catalyst is as follows:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is the ratio of 1:0.3:1, by butyl titanate, oxychlorination
Zirconium and dehydrated alcohol are added in three-necked flask, and then in 60 DEG C of stirred in water bath to complete miscibility, adjusting pH value is 3；
(2) Ti:H is pressed2The molar ratio of O is the ratio of 1:10, is slowly added to deionized water in step (1) mixture, is hydrolyzed into
Gel mixture, after still aging 48h, at 60 DEG C it is dry for 24 hours；
(3) mixture after drying is placed at 550 DEG C and roasts 2h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, ethylenediamine complexing is added, KBH is added in the ratio for being 1:1 in Ni:B molar ratio4
Solution, concentration are that 10 mol/LNaOH solution adjusting pH value is 14, Ni-B plating solution are made, wherein mole of nickel sulfate and ethylenediamine
Than for 1:9；
(5) in the ratio for adding 0.25g in the plating solution of every 100mL, TiO is added in 200mL plating solution2-ZrO2Complex carrier,
Microwave heating 20min at 60 DEG C is washed to neutrality, and alcohol is washed 3 times, and vacuum drying, obtained black solid is nickel boron amorphous state
Alloy catalyst Ni-B/TiO2-ZrO2；
(6) by nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2It is added with the ratio of the rosin after melting in mass ratio 3%
In autoclave, reaction kettle is sealed:
(7) N is used at 0.1MPa2By air displacement 3 times in reaction kettle, then use H2It is replaced 3 times at 0.1MPa, and checks gas
Close property；
(8) H is opened2Intake valve, adjusting reacting kettle inner pressure are 6MPa, are started to warm up, and temperature control is in 170 DEG C, revolving speed
2h is reacted under the conditions of 500r/min, obtains hydrogenated rosin；
(9) after reaction, stop heating, stirring, open kettle after release, catalyst and product are centrifuged；
Product hydrogenated rosin quality analysis results are as follows: conversion ratio 96.52%；Abietic acid 2.06%；Tetrahydroabietic acid 17.98%；Dehydrogenation fir
Acid 1.31%；Acid value 166.2；76.2 DEG C of softening point (ring and ball method).
Embodiment 2: the preparation method and application of this nickel-boron amorphous alloy catalyst is as follows:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is the ratio of 1:0.5:2, by butyl titanate, oxychlorination
Zirconium and dehydrated alcohol are added in three-necked flask, and then in 50 DEG C of stirred in water bath to complete miscibility, adjusting pH value is 2；
(2) Ti:H is pressed2The molar ratio of O is the ratio of 1:20, is slowly added to deionized water in step (1) mixture, is hydrolyzed into
Gel mixture, after still aging 35h, the dry 20h at 80 DEG C；
(3) mixture after drying is placed at 400 DEG C and roasts 4h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, ethylenediamine complexing is added, KBH is added in the ratio for being 1:2 in Ni:B molar ratio4
Solution, concentration are that 10 mol/LNaOH solution adjusting pH value is 10, Ni-B plating solution are made, wherein mole of nickel sulfate and ethylenediamine
Than for 1:3；
(5) in the ratio for adding 1.25g in the plating solution of every 100mL, TiO is added in 200 mL plating solutions2-ZrO2Complex carrier,
The microwave heating 40min at 40 DEG C is washed to neutrality, and alcohol is washed 3 times, and vacuum drying, obtained black solid is nickel boron amorphous
State alloy catalyst Ni-B/TiO2-ZrO2；
(6) by nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2It is added with the ratio of the rosin after melting in mass ratio 5%
In autoclave, reaction kettle is sealed:
(7) N is used at 0.2 mpa2By air displacement 3 times in reaction kettle, then use H2It replaces 3 times at 0.2 mpa, and checks gas
Close property；
(8) H is opened2Intake valve, adjusting reacting kettle inner pressure are 3MPa, are started to warm up, and temperature control is in 180 DEG C, revolving speed
3h is reacted under the conditions of 600r/min, obtains hydrogenated rosin；
(9) after reaction, stop heating, stirring, open kettle after release, catalyst and product are centrifuged；
Product hydrogenated rosin quality analysis results are as follows: conversion ratio 94.33%；Abietic acid 2.14%；Tetrahydroabietic acid 17.47%；Dehydrogenation fir
Acid 2.18%；Acid value 166.9；76.7 DEG C of softening point (ring and ball method)
Embodiment 3: the preparation method and application of this nickel-boron amorphous alloy catalyst is as follows:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is the ratio of 1:1:3, by butyl titanate, zirconium oxychloride
It is added in three-necked flask with dehydrated alcohol, then in 40 DEG C of stirred in water bath to complete miscibility, adjusting pH value is 3；
(2) Ti:H is pressed2The molar ratio of O is the ratio of 1:30, is slowly added to deionized water in step (1) mixture, is hydrolyzed into
Gel mixture, after still aging 30h, the dry 15h at 90 DEG C；
(3) mixture after drying is placed at 450 DEG C and roasts 3h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, ethylenediamine complexing is added, KBH is added in the ratio for being 1:3 in Ni:B molar ratio4
Solution, concentration are that 10 mol/LNaOH solution adjusting pH value is 11, Ni-B plating solution are made, wherein mole of nickel sulfate and ethylenediamine
Than for 1:5；
(5) in the ratio for adding 0.75g in the plating solution of every 100mL, TiO is added in 200 mL plating solutions2-ZrO2Complex carrier,
The microwave heating 30min at 50 DEG C is washed to neutrality, and alcohol is washed 3 times, and vacuum drying, obtained black solid is nickel boron amorphous
State alloy catalyst Ni-B/TiO2-ZrO2；
(6) by nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2Add with the ratio of the rosin after melting in mass ratio 10%
Enter in autoclave, seal reaction kettle:
(7) N is used at 0.4MPa2By air displacement 3 times in reaction kettle, then use H2It is replaced 3 times at 0.4MPa, and checks gas
Close property；
(8) H is opened2Intake valve, adjusting reacting kettle inner pressure are 4MPa, are started to warm up, and temperature control is in 200 DEG C, revolving speed
2h is reacted under the conditions of 1000r/min, obtains hydrogenated rosin；
(9) after reaction, stop heating, stirring, open kettle after release, catalyst and product are centrifuged；
Product hydrogenated rosin quality analysis results are as follows: conversion ratio 98.22%；Abietic acid 0.94%；Tetrahydroabietic acid 18.98%；Dehydrogenation fir
Acid 1.94%；Acid value 168.2；77.2 DEG C of softening point (ring and ball method).
Embodiment 4: the preparation method and application of this nickel-boron amorphous alloy catalyst is as follows:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is the ratio of 1:0.6:5, by butyl titanate, oxychlorination
Zirconium and dehydrated alcohol are added in three-necked flask, and then in 45 DEG C of stirred in water bath to complete miscibility, adjusting pH value is 4；
(2) Ti:H is pressed2The molar ratio of O is the ratio of 1:15, is slowly added to deionized water in step (1) mixture, is hydrolyzed into
Gel mixture, it is still aging for 24 hours after, the dry 12h at 100 DEG C；
(3) mixture after drying is placed at 500 DEG C and roasts 2h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, ethylenediamine complexing is added, the ratio for being 1:1.5 in Ni:B molar ratio is added
KBH4Solution, concentration are that adjust pH value be 12 to 10 mol/LNaOH solution, Ni-B plating solution is made, wherein nickel sulfate and ethylenediamine
Molar ratio is 1:7；
(5) in the ratio for adding 0.5g in the plating solution of every 100 mL, TiO is added in 200 mL plating solutions2-ZrO2Complex carrier,
The microwave heating 25min at 55 DEG C is washed to neutrality, and alcohol is washed 3 times, and vacuum drying, obtained black solid is nickel boron amorphous
State alloy catalyst Ni-B/TiO2-ZrO2；
(6) by nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2It is added with the ratio of the rosin after melting in mass ratio 8%
In autoclave, reaction kettle is sealed:
(7) N is used at 0.5MPa2By air displacement 3 times in reaction kettle, then use H2It is replaced 3 times at 0.5MPa, and checks gas
Close property；
(8) H is opened2Intake valve, adjusting reacting kettle inner pressure are 6MPa, are started to warm up, and temperature control is in 170 DEG C, revolving speed
4h is reacted under the conditions of 1000r/min, obtains hydrogenated rosin；
(9) after reaction, stop heating, stirring, open kettle after release, catalyst and product are centrifuged；
Product hydrogenated rosin quality analysis results are as follows: conversion ratio 98.62%；Abietic acid 1.02%；Tetrahydroabietic acid 19.26%；Dehydrogenation fir
Acid 1.24%；Acid value 170.5；77.2 DEG C of softening point (ring and ball method).
Embodiment 5: the preparation method and application of this nickel-boron amorphous alloy catalyst is as follows:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is the ratio of 1:0.6:2, by butyl titanate, oxychlorination
Zirconium and dehydrated alcohol are added in three-necked flask, and then in 60 DEG C of stirred in water bath to complete miscibility, adjusting pH value is 2；
(2) Ti:H is pressed2The molar ratio of O is the ratio of 1:25, is slowly added to deionized water in step (1) mixture, is hydrolyzed into
Gel mixture, after still aging 35h, the dry 15h at 75 DEG C；
(3) mixture after drying is placed at 500 DEG C and roasts 3h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, ethylenediamine complexing is added, KBH is added in the ratio for being 1:3 in Ni:B molar ratio4
Solution, concentration are that 10 mol/LNaOH solution adjusting pH value is 10, Ni-B plating solution are made, wherein mole of nickel sulfate and ethylenediamine
Than for 1:4；
(5) in the ratio for adding 1g in the plating solution of every 100 mL, TiO is added in 200 mL plating solutions2-ZrO2Complex carrier,
Microwave heating 35min at 40 DEG C is washed to neutrality, and alcohol is washed 3 times, and vacuum drying, obtained black solid is nickel boron amorphous state
Alloy catalyst Ni-B/TiO2-ZrO2；
(6) by nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2It is added with the ratio of the rosin after melting in mass ratio 4%
In autoclave, reaction kettle is sealed:
(7) N is used at 0.5MPa2By air displacement 3 times in reaction kettle, then use H2It is replaced 3 times at 0.5MPa, and checks gas
Close property；
(8) H is opened2Intake valve, adjusting reacting kettle inner pressure are 4MPa, are started to warm up, and temperature control is in 190 DEG C, revolving speed
3h is reacted under the conditions of 500r/min, obtains hydrogenated rosin；
(9) after reaction, stop heating, stirring, open kettle after release, catalyst and product are centrifuged；
Product hydrogenated rosin quality analysis results are as follows: conversion ratio 99.84%；Abietic acid 0.09%；Tetrahydroabietic acid 20.23%；Dehydrogenation fir
Acid 0.75%；Acid value 170.7；77.8 DEG C of softening point (ring and ball method).
(10) catalyst that centrifugation obtains is washed with dehydrated alcohol, after vacuum dried, continue rosin and add hydrogen, turned
Rate is 99.56%；After repeating 9 experiments, conversion ratio 97.62%, and after the 10th time, conversion ratio 95.37%.
Therefore catalyst stability is good, and the service life is long, can carry out 9~10 rosin Hydrogenation Experiments, after 10 times conversion ratio still 95% with
On.
Claims (5)
1. a kind of preparation method of nickel-boron amorphous alloy catalyst, it is characterised in that: the following steps are included:
(1) in butyl titanate: zirconium oxychloride: the molar ratio of dehydrated alcohol is 1:(0.3~1): the ratio of (1~5), by metatitanic acid fourth
Ester, zirconium oxychloride and dehydrated alcohol are added in three-necked flask, then in 40~60 DEG C of stirred in water bath to complete miscibility, adjust pH
Value is 2~4；
(2) Ti:H is pressed2The molar ratio of O be 1:(10~30) ratio, be slowly added to deionized water in step (1) mixture, it is quiet
After setting 24~48h of ageing, dry 12 at 60~100 DEG C~for 24 hours；
(3) mixture after drying is placed at 400~550 DEG C and roasts 2~4h to get TiO2-ZrO2Complex carrier；
(4) nickel sulfate is dissolved in deionized water, be added ethylenediamine complexing, by Ni:B molar ratio be 1:(1~3) ratio, add
Enter KBH4Solution, it is 10~14 that NaOH solution, which adjusts pH value, and Ni-B plating solution is made, and wherein the molar ratio of nickel sulfate and ethylenediamine is
1:(3~9)；
(5) TiO is added in the plating solution2-ZrO2Complex carrier, 20~40min of microwave heating at 40~60 DEG C, in being washed to
Property, alcohol washes, and is dried in vacuo, and obtained black solid is nickel-boron amorphous alloy catalyst n i-B/TiO2-ZrO2。
2. the preparation method of nickel-boron amorphous alloy catalyst according to claim 1, it is characterised in that: NaOH solution is dense
Degree is 10 mol/L.
3. the preparation method of nickel-boron amorphous alloy catalyst according to claim 1, it is characterised in that: every 100mL's
The TiO of 0.25~1.25 g is added in plating solution2-ZrO2Complex carrier.
4. nickel boron amorphous state made from the preparation method of the described in any item nickel-boron amorphous alloy catalyst of claim 1-3 is closed
Au catalyst.
5. application of the nickel-boron amorphous alloy catalyst as claimed in claim 4 in rosin hydrogenation reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382559A (en) * | 2022-08-30 | 2022-11-25 | 湘潭大学 | Bifunctional catalyst for hydrodeoxygenation reaction and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546229A (en) * | 2003-12-15 | 2004-11-17 | 南开大学 | Catalyst for porous support carried NiB amorphous alloy and preparation method thereof |
| CN1737196A (en) * | 2005-09-09 | 2006-02-22 | 桂林工学院 | Technique for compositely coating Ni-B-nanometer TiO2 chemically |
| CN101015804A (en) * | 2007-03-09 | 2007-08-15 | 南开大学 | Swollen vermiculite loading NiB amorphous alloy catalyst, its prepn. method and application |
| US20080009640A1 (en) * | 2005-10-24 | 2008-01-10 | Wei Li | Supported amorphous ni-b alloy catalyst, its preparation and use |
| US20120107627A1 (en) * | 2009-06-29 | 2012-05-03 | Wei Gao | Plating or Coating Method for Producing Metal-Ceramic Coating on a Substrate |
| US8642496B2 (en) * | 2010-07-13 | 2014-02-04 | Agency For Science, Technology And Research | Method for forming a catalyst comprising catalytic nanoparticles and a catalyst support |
| CN105727957A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院大连化学物理研究所 | Loaded type iron-nickel phosphide catalyst material and application thereof |
-
2018
- 2018-09-26 CN CN201811121120.1A patent/CN109433209A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546229A (en) * | 2003-12-15 | 2004-11-17 | 南开大学 | Catalyst for porous support carried NiB amorphous alloy and preparation method thereof |
| CN1737196A (en) * | 2005-09-09 | 2006-02-22 | 桂林工学院 | Technique for compositely coating Ni-B-nanometer TiO2 chemically |
| US20080009640A1 (en) * | 2005-10-24 | 2008-01-10 | Wei Li | Supported amorphous ni-b alloy catalyst, its preparation and use |
| CN101015804A (en) * | 2007-03-09 | 2007-08-15 | 南开大学 | Swollen vermiculite loading NiB amorphous alloy catalyst, its prepn. method and application |
| US20120107627A1 (en) * | 2009-06-29 | 2012-05-03 | Wei Gao | Plating or Coating Method for Producing Metal-Ceramic Coating on a Substrate |
| US8642496B2 (en) * | 2010-07-13 | 2014-02-04 | Agency For Science, Technology And Research | Method for forming a catalyst comprising catalytic nanoparticles and a catalyst support |
| CN105727957A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院大连化学物理研究所 | Loaded type iron-nickel phosphide catalyst material and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| LING LAN ET AL.: "Synthesis of a Supported Amorphous Ni-B/TiO2-Al2O3 Alloy Catalyst by Electroless Plating", 《ADVANCED MATERIALS RESEARCH》 * |
| 南京林产工业学院主编: "《天然树脂生产工艺学》", 31 December 1983, 中国林业出版社 * |
| 吕志果等: "负载型纳米非晶合金NiB/MCM-41催化松香加氢反应性能研究", 《林产化学与工业》 * |
| 石秋杰等: "糠醛液相加氢用Mo改性Ni-B/TiO2-Al2O3(S)非晶态合金催化剂", 《物理化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382559A (en) * | 2022-08-30 | 2022-11-25 | 湘潭大学 | Bifunctional catalyst for hydrodeoxygenation reaction and preparation method and application thereof |
| CN115382559B (en) * | 2022-08-30 | 2023-09-22 | 湘潭大学 | Double-function catalyst for hydrodeoxygenation reaction and preparation method and application thereof |
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