CN109395753A - A kind of preparation method and application of catalyst for hydrogenation - Google Patents
A kind of preparation method and application of catalyst for hydrogenation Download PDFInfo
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- CN109395753A CN109395753A CN201811121386.6A CN201811121386A CN109395753A CN 109395753 A CN109395753 A CN 109395753A CN 201811121386 A CN201811121386 A CN 201811121386A CN 109395753 A CN109395753 A CN 109395753A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 229910018104 Ni-P Inorganic materials 0.000 claims abstract description 18
- 229910018536 Ni—P Inorganic materials 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000001632 sodium acetate Substances 0.000 claims abstract description 8
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 52
- 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 abstract description 42
- 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 abstract description 42
- 238000000034 method Methods 0.000 abstract description 12
- 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
- 239000002253 acid Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 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 10
- 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 10
- 238000002474 experimental method Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 meanwhile Chemical compound 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
Abstract
The present invention discloses a kind of preparation method of catalyst for hydrogenation, belongs to chemical industry catalysis technical field；This method is to mix graphene oxide dispersion with nickel chloride solution, and sodium acetate is added in mixed solution, is then diluted with deionized water, ultrasonic disperse；Sodium borohydride, sodium hypophosphite solution reaction are added under the conditions of nitrogen, 70 ~ 90 DEG C after adjusting pH, is stirred continuously to bubble-free when generating and stops reaction, Ni-P/rGO catalyst for hydrogenation is made in filtration drying；The preparation method of catalyst for hydrogenation of the present invention is simple, low in cost and have a longer life expectancy, and is used in catalytic hydrogenation of rosin reaction, abietic type acid's high conversion rate, tetrahydroabietic acid selectivity is high.
Description
Technical field
The present invention relates to a kind of preparation method and applications of catalyst for hydrogenation, belong to chemical field.
Background technique
Rosin is the natural resin being widely present in a kind of nature, and China's rosin annual output occupy first place in the world.It is led
Wanting ingredient is abietic type acid.Industrial hydrogenated rosin generally adds hydrogen to be made by rosin, is widely used in adhesive, synthesis rubber
The industrial departments such as glue, coating, ink, papermaking, electronics, food.
Graphene is a kind of New Two Dimensional material, has high-specific surface area, easily dispersion, high-mechanical property and thermal stability etc.
Feature, the oxygen-containing group that the graphene surface of chemical method preparation can have some carbon vacancy and not be reduced, this is unfavorable for electricity
Son migration, but this has unique performance in catalytic field synthesis metal-graphite alkene material to graphene, meanwhile, graphene is multiple
The effect of the π-π between graphene sheet layer can be weakened by closing nanoparticle, so that it be made to be not easy to stack, nanoparticle also has with it
Coupling is cooperateed with, this is conducive to prepare the good catalyst of dispersed high catalytic performance.
For rosin hydrogenation catalyst mainly based on Pd system, Ni series catalysts, Pd series catalysts have added hydrogen for rosin at present
There is higher catalytic, but it is there may be preparation process complexity, cost of manufacture is high, hydrogenation reaction process conditions are higher or easy
The disadvantages of poisoning.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of catalyst for hydrogenation, the specific steps are as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution；
(2) Na is pressed+:Ni2+Molar ratio is the ratio of 1:3 ~ 20, and sodium acetate is added in step (1) mixed solution, is then spent
Ionized water dilutes 10 ~ 15 times, ultrasonic disperse 20min；
It (3) is 9 ~ 13 with sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 70 ~ 90 DEG C that sodium borohydride, sodium hypophosphite solution are added into three-necked flask, is stirred continuously to bubble-free
Stop reaction when generation, Ni-P/rGO catalyst for hydrogenation is made in filtration drying.
The graphene oxide and nickel chloride mass ratio are 1:3 ~ 20.
The Ni:NaBH4Molar ratio be 20 ~ 30:1, the molar ratio of Ni:P is 1:3 ~ 7.
The concentration of the sodium hypophosphite solution is 1 mol/L.
The present invention adds hydrogen in rosin another object is that applying Ni-P/rGO catalyst for hydrogenation made from the above method
In reaction, the specific steps are as follows:
(1) rosin is weighed, Ni-P/rGO catalyst for hydrogenation is weighed by the 3 ~ 10% of rosin quality and is added in reaction kettle, sealing
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) it opens valve and is filled with H2, adjust 3 ~ 6MPa of reacting kettle inner pressure and close valve；It begins to warm up, temperature is 180 ~ 220
DEG C, revolving speed be 600 ~ 1000r/min under the conditions of react 3 ~ 7h, hydrogenated rosin is obtained by filtration.
The advantages of the method for the present invention:
(1) Ni-P/rGO composite catalyst is made using the method for a step electronation in the present invention, easy to operate, low in cost,
And the catalyst of preparation has that dispersibility, the structural advantages such as have good uniformity.
(2) Ni-P/rGO composite catalyst prepared by the present invention is applied in rosin hydrogenation system, compared to its in document
His Ni series catalysts have the advantages such as high conversion rate, tetrahydroabietic acid selectivity height, long service life.
Specific embodiment
Below by embodiment, the invention will be further described, but the invention is not limited to these examples.
Embodiment 1: the preparation method and application of this catalyst for hydrogenation is as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution, wherein graphene oxide and nickel chloride mass ratio are 1:3,
Graphene oxide dispersion concentration is 5g/L, and chlorination nickel concentration is 1mol/L；
(2) Na is pressed+:Ni2+Molar ratio be 1:20 ratio, sodium acetate is added in step (1) mixed solution, then spend from
Sub- water dilutes 10 times, ultrasonic disperse 20min；
It (3) is 9 with 10mol/L sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 90 DEG C being added sodium borohydride into three-necked flask as initiator, 1mol/L sodium hypophosphite is then added
Solution is stirred continuously to bubble-free when generating and stops reaction, and Ni-P/rGO catalyst for hydrogenation is made in filtration drying, wherein
Ni:NaBH4Molar ratio be 25:1, the molar ratio of Ni:P is 1:7；
(6) rosin is weighed, Ni-P/rGO catalyst for hydrogenation is weighed by the 3% of rosin quality and is added in reaction kettle, sealing reaction
Kettle；
(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) it opens valve and is filled with H2, adjusting reacting kettle inner pressure is that 6MPa closes valve；180 DEG C are heated to, is in revolving speed
7h is reacted under the conditions of 600r/min, is filtered, filtrate is hydrogenated rosin；
It is as follows that reaction product hydrogenates rosin quality analysis result: conversion ratio 98.38%；Abietic acid 1.36%；Tetrahydroabietic acid 18.25%；
Dehydrogenation abietic acid 1.55%；Acid value 170；76.6 DEG C of softening point (ring and ball method).
(9) catalyst is washed three times with dehydrated alcohol, is dried in vacuo 2h, continues rosin hydrogenation reaction, repeats 10
After secondary experiment, conversion ratio 96.66%, therefore catalyst stability is good, the service life is long, and conversion ratio is still after 10 rosin Hydrogenation Experiments
96% or more.
Embodiment 2: the preparation method and application of this catalyst for hydrogenation is as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution, wherein graphene oxide and nickel chloride mass ratio are 1:7,
Graphene oxide dispersion concentration is 5g/L, and chlorination nickel concentration is 1mol/L；
(2) Na is pressed+:Ni2+Molar ratio be 1:17 ratio, sodium acetate is added in step (1) mixed solution, then spend from
Sub- water dilutes 12 times, ultrasonic disperse 20min；
It (3) is 11 with 10mol/L sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 85 DEG C being added sodium borohydride into three-necked flask as initiator, 1mol/L sodium hypophosphite is then added
Solution is stirred continuously to bubble-free when generating and stops reaction, and Ni-P/rGO catalyst for hydrogenation is made in filtration drying, wherein
Ni:NaBH4Molar ratio be 20:1, the molar ratio of Ni:P is 1:4.
(6) rosin is weighed, Ni-P/rGO catalyst for hydrogenation is weighed by the 5% of rosin quality and is added in reaction kettle, sealing
Reaction kettle；
(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) it opens valve and is filled with H2, adjusting reacting kettle inner pressure is that 5.5MPa closes valve；190 DEG C are heated to, is in revolving speed
6h is reacted under the conditions of 800r/min, is filtered, filtrate is hydrogenated rosin；
It is as follows that reaction product hydrogenates rosin quality analysis result: conversion ratio 99.32%；Abietic acid 0.56%；Tetrahydroabietic acid 18.56%；It goes
Hydrogen abietic acid 1.45%；Acid value 166；77.5 DEG C of softening point (ring and ball method).
(9) catalyst is washed three times with dehydrated alcohol, is dried in vacuo 2h, continues rosin hydrogenation reaction, repeats 10
After secondary experiment, conversion ratio 97.56%, therefore catalyst stability is good, the service life is long, and conversion ratio is still after 10 rosin Hydrogenation Experiments
97% or more.
Embodiment 3: the preparation method and application of this catalyst for hydrogenation is as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution, wherein graphene oxide and nickel chloride mass ratio are 1:11,
Graphene oxide dispersion concentration is 5g/L, and chlorination nickel concentration is 1mol/L；
(2) Na is pressed+:Ni2+Molar ratio be 1:15 ratio, sodium acetate is added in step (1) mixed solution, then spend from
Sub- water dilutes 13 times, ultrasonic disperse 20min；
It (3) is 12 with 10mol/L sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 80 DEG C being added sodium borohydride into three-necked flask as initiator, 1mol/L sodium hypophosphite is then added
Solution is stirred continuously to bubble-free when generating and stops reaction, and Ni-P/rGO catalyst for hydrogenation is made in filtration drying, wherein
Ni:NaBH4Molar ratio be 30:1, the molar ratio of Ni:P is 1:5.
(6) rosin is weighed, Ni-P/rGO catalyst for hydrogenation is weighed by the 8% of rosin quality and is added in reaction kettle, sealing
Reaction kettle；
(7) N is used at 0.3MPa2By air displacement 3 times in reaction kettle, then use H2It is replaced 3 times at 0.3MPa, and checks gas
Close property；
(8) it opens valve and is filled with H2, adjusting reacting kettle inner pressure is that 4.5MPa closes valve；200 DEG C are heated to, is in revolving speed
4h is reacted under the conditions of 900r/min, is filtered, filtrate is hydrogenated rosin；
It is as follows that reaction product hydrogenates rosin quality analysis result: conversion ratio 98.35%；Abietic acid 1.35%；Tetrahydroabietic acid 17.52%；It goes
Hydrogen abietic acid 1.87%；Acid value 165.5；76.5 DEG C of softening point (ring and ball method).
(9) catalyst is washed three times with dehydrated alcohol, is dried in vacuo 2h, continues rosin hydrogenation reaction, repeats 10
After secondary experiment, conversion ratio 96.35%, therefore catalyst stability is good, the service life is long, and conversion ratio is still after 10 rosin Hydrogenation Experiments
96% or more.
Embodiment 4: the preparation method and application of this catalyst for hydrogenation is as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution, wherein graphene oxide and nickel chloride mass ratio are 1:15,
Graphene oxide dispersion concentration is 5g/L, and chlorination nickel concentration is 1mol/L；
(2) Na is pressed+:Ni2+Molar ratio be 1:5 ratio, sodium acetate is added in step (1) mixed solution, then spend from
Sub- water dilutes 14 times, ultrasonic disperse 20min；
It (3) is 13 with 10mol/L sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 75 DEG C being added sodium borohydride into three-necked flask as initiator, 1mol/L sodium hypophosphite is then added
Solution is stirred continuously to bubble-free when generating and stops reaction, and Ni-P/rGO catalyst for hydrogenation is made in filtration drying, wherein
Ni:NaBH4Molar ratio be 22:1, the molar ratio of Ni:P is 1:6.
(6) rosin is weighed, Ni-P/rGO catalyst for hydrogenation is weighed by the 9% of rosin quality and is added in reaction kettle, sealing
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) it opens valve and is filled with H2, adjusting reacting kettle inner pressure is that 4MPa closes valve；210 DEG C are heated to, is in revolving speed
3h is reacted under the conditions of 1000r/min, is filtered, filtrate is hydrogenated rosin；
It is as follows that reaction product hydrogenates rosin quality analysis result: conversion ratio 97.40%；Abietic acid 2.11%；Tetrahydroabietic acid 16.18%；It goes
Hydrogen abietic acid 1.25%；Acid value 168.1；75.9 DEG C of softening point (ring and ball method).
(9) catalyst is washed three times with dehydrated alcohol, is dried in vacuo 2h, continues rosin hydrogenation reaction, repeats 10
After secondary experiment, conversion ratio 96.07%, therefore catalyst stability is good, the service life is long, and conversion ratio is still after 10 rosin Hydrogenation Experiments
96% or more.
Embodiment 5: the preparation method and application of this catalyst for hydrogenation is as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution, wherein graphene oxide and nickel chloride mass ratio are 1:20,
Graphene oxide dispersion concentration is 5g/L, and chlorination nickel concentration is 1mol/L；
(2) Na is pressed+:Ni2+Molar ratio be 1:3 ratio, sodium acetate is added in step (1) mixed solution, then spend from
Sub- water dilutes 15 times, ultrasonic disperse 20min；
It (3) is 9 with 10mol/L sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 70 DEG C being added sodium borohydride into three-necked flask as initiator, 1mol/L sodium hypophosphite is then added
Solution is stirred continuously to bubble-free when generating and stops reaction, and Ni-P/rGO catalyst for hydrogenation is made in filtration drying, wherein
Ni:NaBH4Molar ratio be 26:1, the molar ratio of Ni:P is 1:3.
(6) rosin is weighed, Ni-P/rGO catalyst for hydrogenation is weighed by the 10% of rosin quality and is added in reaction kettle, it is close
Seal reaction kettle；
(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) it opens valve and is filled with H2, adjusting reacting kettle inner pressure is that 3MPa closes valve；220 DEG C are heated to, is in revolving speed
3h is reacted under the conditions of 700r/min, is filtered, filtrate is hydrogenated rosin；
It is as follows that reaction product hydrogenates rosin quality analysis result: conversion ratio 96.25%；Abietic acid 3.01%；Tetrahydroabietic acid 16.07%；It goes
Hydrogen abietic acid 1.38%；Acid value 169.2；76.5 DEG C of softening point (ring and ball method)；
(9) catalyst is washed three times with dehydrated alcohol, is dried in vacuo 2h, continues rosin hydrogenation reaction, be repeated 10 times reality
After testing, conversion ratio 94.25%, therefore catalyst stability is good, the service life is long, and conversion ratio is still 94% after 10 rosin Hydrogenation Experiments
More than.
Claims (4)
1. a kind of preparation method of catalyst for hydrogenation, which is characterized in that specific step is as follows:
(1) graphene oxide dispersion is mixed with nickel chloride solution；
(2) Na is pressed+:Ni2+Molar ratio is the ratio of 1:3 ~ 20, and sodium acetate is added in step (1) mixed solution, is then spent
Ionized water dilutes 10 ~ 15 times, ultrasonic disperse 20min；
It (3) is 9 ~ 13 with sodium hydroxide solution regulating step (2) mixed solution pH value；
(4) mixed solution pours into three-necked flask after adjusting pH, and moves in oil bath pan, is added under the atmosphere of nitrogen
Heat；
(5) it is heated to after 70 ~ 90 DEG C that sodium borohydride, sodium hypophosphite solution are added into three-necked flask, is stirred continuously to bubble-free
Stop reaction when generation, Ni-P/rGO catalyst for hydrogenation is made in filtration drying.
2. the preparation method of catalyst for hydrogenation according to claim 1, it is characterised in that: graphene oxide and chlorination
Nickel mass ratio is 1:3 ~ 20.
3. the preparation method of catalyst for hydrogenation according to claim 1, it is characterised in that: Ni:NaBH4Molar ratio
For 20 ~ 30:1, the molar ratio of Ni:P is 1:3 ~ 7.
4. Ni-P/rGO catalyst for hydrogenation is in pine made from the preparation method of catalyst for hydrogenation described in claim 1
Application in fragrant hydrogenation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811121386.6A CN109395753B (en) | 2018-09-26 | 2018-09-26 | Preparation method and application of hydrogenation reaction catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811121386.6A CN109395753B (en) | 2018-09-26 | 2018-09-26 | Preparation method and application of hydrogenation reaction catalyst |
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| Publication Number | Publication Date |
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| CN109395753A true CN109395753A (en) | 2019-03-01 |
| CN109395753B CN109395753B (en) | 2021-07-16 |
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