CN106268824B - A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof - Google Patents
A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof Download PDFInfo
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- CN106268824B CN106268824B CN201610642488.7A CN201610642488A CN106268824B CN 106268824 B CN106268824 B CN 106268824B CN 201610642488 A CN201610642488 A CN 201610642488A CN 106268824 B CN106268824 B CN 106268824B
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- 239000003208 petroleum Substances 0.000 title claims abstract description 26
- 229920005989 resin Polymers 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007868 Raney catalyst Substances 0.000 title claims abstract description 10
- 229910000564 Raney nickel Inorganic materials 0.000 title claims abstract description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 8
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims description 28
- 230000032683 aging Effects 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003863 metallic catalyst Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- HKIQZBZCKQBMJT-UHFFFAOYSA-J nickel(2+) disulfate Chemical compound [Ni++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HKIQZBZCKQBMJT-UHFFFAOYSA-J 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000008601 oleoresin Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
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- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to metallic catalyst preparation fields, and in particular to a kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof.The catalyst includes the diatomite support handled through expanding agent and is supported on supported catalyst Ni, and expanding agent is selected from one or more of sodium citrate, polyvinylpyrrolidone, polyvinyl acetate.In addition, the invention also discloses the preparation methods of the catalyst.The catalyst can reduce interior diffusion for C5 hydrogenation of petroleum resin, and dosage is few, and activity is high, and the service life is long, the C5 hydrogenated petroleum resin of water white high-quality can be made, and preparation process is simple, be suitble to industrialized production.
Description
[technical field]
The present invention relates to metallic catalyst preparation technical fields, and in particular to a kind of C5 hydrogenation of petroleum resin Raney nickel
And preparation method thereof.
[background technique]
C5 Petropols be using C 5 fraction as raw material it is aggregated obtained by thermoplastic resin, be molecular weight be about 300-3000
Oligomer, exist at room temperature with glassy state.The C5 Petropols of synthesis cause due to containing unsaturated bond in use process
In the problems such as there are stink, form and aspect to deepen, photo and thermal stability is poor, which greatly limits the application range of C5 Petropols and economy
Benefit.Add hydrogen to be the common method for preparing light high-quality Petropols, obtained C5 hydrogenated petroleum resin have color number it is low,
The advantages that light and heat stability is that high-grade dedicated Petropols can also be wide not only with the general service of common C5 Petropols
General to apply in the field that food packaging, pressure sensitive adhesive, transparent sealant etc. have more high additive value, therefore, the market price is about
It is 15000 yuan/ton, is 2-3 times of common petroleum resin.By adding hydrogen, not only expand the application range of C5 Petropols, and mentions
High economic benefit.
Petropols molecular weight is larger and structure is in chain and ring-type, causes its steric hindrance larger, Petropols molecule
It is difficult to enter inside catalyst granules, there are apparent inside diffusional resistance, conventional or too small catalyst aperture is almost without adding
Hydrogen activity；C5 hydrogenation of petroleum resin is along with exothermic effect, and catalyst duct is too small to be unfavorable for radiating, and carbon distribution easy to form makes to urge
Agent activity and stability degradation, therefore inside diffusional resistance can be reduced to catalyst progress reaming, it is conducive to heat dissipation, improves C5
Petropols catalytic hydrogenation reaction rate improves catalyst utilization and stability, reduces old.Currently, C5 Petropols add
Hydrogen mainly uses the loaded noble metal catalysts such as Pd, Pt, not only expensive, and easily poisoning, and stability is bad, also there is part
It is reported using the research of the non-precious metal catalysts such as Ni, W, but Ni, W dosage are larger and auxiliary agent or complexing agent need to be added, and therefore, grind
Issue a kind of dosage it is few, it is active it is high, stability is good, non-precious metal catalyst capable of being industrialized produces China's C5 hydrogenation of petroleum resin
The development of industry is most important.
[summary of the invention]
Goal of the invention of the invention is: in view of the above-mentioned problems, provide a kind of C5 hydrogenation of petroleum resin Raney nickel and
Preparation method, the catalyst duct is big, can reduce inside diffusional resistance；Good dispersion, dosage is few, at low cost；For C5 stone
Oleoresin hydrogenation activity is high, and stability is good, the C5 hydrogenated petroleum resin of water white high-quality can be made, and preparation process is simple,
It is suitable for industrialized production.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of C5 hydrogenation of petroleum resin Raney nickel comprising the diatomite support handled through expanding agent and is supported on load
Catalyst n i on body, expanding agent are selected from one or more of sodium citrate, polyvinylpyrrolidone, polyvinyl acetate.
Preferably, weight of the mass percentage of the Ni based on the carrier is 8-18%.
Preferably, weight of the mass percentage of the expanding agent based on carrier is 3-8%.
Preferably, the polyvinylpyrrolidone is selected from one or more of PVPK12-PVPK30.
Preferably, the polyvinyl acetate is selected from one of polyvinyl acetate that molecular weight is 2000-25000 or several
Kind.
The preparation method of C5 hydrogenation of petroleum resin Raney nickel of the invention a kind of the following steps are included: (1) by reaming
Agent is dissolved in deionized water or ethyl alcohol, and heating pressurization unsaturation impregnates 3-6h in the autoclave with stirring with carrier diatomaceous earth,
Sample is at room temperature after aging 2h after dipping, the dry 7-12h in 70-100 DEG C of baking oven, then in 400-650 DEG C of Muffle furnace
Roasting 3.5-6.5h obtains spare carrier, and Muffle furnace heating rate is 2 DEG C/min；(2) nickel salt is dissolved in deionized water, is adjusted
Solution ph is 1.8-2.3；(3) nickel salt solution and spare carrier are heated into the unsaturated dipping of pressurization in the autoclave with stirring
8-12h, sample is at room temperature after aging 2-4h after dipping, the dry 7-12h in 70-100 DEG C of baking oven, it is dry after sample be placed in
Reductase 12-3h is in 400-500 DEG C of atmosphere of hydrogen to get C5 hydrogenation of petroleum resin catalyst；
Three kind mixing of the Ni in nickel nitrate, nickel acetylacetonate, nickel formate, nickel acetate, nickel chloride, nickel sulfate
Nickel salt.
Dipping temperature is 60-120 DEG C in the step (1), impregnation pressure 0.3-2.5MPa.
Dipping temperature is 50-80 DEG C in the step (3), impregnation pressure 0.3-1MPa.
The method of evaluating performance of a kind of C5 hydrogenation of petroleum resin Raney nickel of the invention are as follows: C5 Petropols are complete
It is dissolved in hexamethylene, mass fraction 10-35%, C5 Petropols material liquid is put into reaction under high pressure together with catalyst
Kettle is 5-8MPa in reaction pressure, and reaction temperature reacts 4-5h under conditions of being 250-270 DEG C, and the quality of the catalyst is
The 6-10% of C5 Petropols quality.
The present invention carries out expanding treatment to carrier by expanding agent, can reduce C5 hydrogenation of petroleum resin inside diffusional resistance, mention
High catalyst utilization rate reduces catalyst amount；Absorption and desorption conducive to reactant and product, conducive to the expansion of reaction heat
It dissipates, improves catalyst activity and stability；By the unsaturated dipping of heating pressurization, nickel active component is made to be evenly distributed on carrier
On, improve the dispersion degree of nickel active component；By the pH value and drying temperature of the maceration extract in control preparation process, thin is obtained
The nickel active component of grain high degree of dispersion is conducive to the utilization rate and stability that improve catalyst.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are: the catalyst duct is big,
Inside diffusional resistance can be reduced；Good dispersion, dosage is few, at low cost；High for C5 hydrogenation of petroleum resin activity, stability is good, can
The C5 hydrogenated petroleum resin of water white high-quality is made, and preparation process is simple, is suitable for industrialized production.
[specific embodiment]
For a better understanding of the present invention, below with specific example come the technical solution that the present invention will be described in detail, but this
Invention is not limited thereto.
Embodiment 1
The catalyst of the present embodiment comprising the diatomite support handled through expanding agent and is supported on supported catalyst
Weight of the mass percentage of Ni, Ni based on the carrier is 8%, and expanding agent is sodium citrate, the quality percentage of expanding agent
Weight of the content based on carrier is 8%.
The preparation method of the catalyst of the present embodiment the following steps are included: sodium citrate is dissolved in deionized water by (1), with
Carrier diatomaceous earth unsaturated dipping 6h, dipping temperature in autoclave are 60 DEG C, impregnation pressure 2.5MPa, and sample exists after dipping
At room temperature after aging 2h, dry 7h, then obtains spare carrier, horse in 650 DEG C of Muffle kiln roasting 3.5h in 100 DEG C of baking ovens
Not furnace heating rate is 2 DEG C/min；(2) nickel formate, nickel acetate, nickel chloride mixing nickel salt are dissolved in deionized water, are adjusted molten
Liquid pH value is 1.8；(3) by nickel salt solution and spare carrier, unsaturated dipping 12h, dipping temperature are 80 DEG C in autoclave, leaching
Stain pressure is 0.3MPa, and sample is at room temperature after aging 4h after dipping, the dry 7h in 100 DEG C of baking ovens, it is dry after sample be placed in
3h is restored in 400 DEG C of atmosphere of hydrogen to get C5 hydrogenation of petroleum resin catalyst；
The catalyst performance evaluation method of the present embodiment are as follows: C5 Petropols are dissolved completely in hexamethylene, quality point
Number is 10%, and C5 Petropols material liquid is put into autoclave together with catalyst, is 5MPa, reaction temperature in reaction pressure
Degree reacts 4h under conditions of being 270 DEG C, the quality of the catalyst is the 10% of C5 Petropols quality.
The results are shown in Table 1 for catalyst performance evaluation.
Embodiment 2
The catalyst of the present embodiment comprising the diatomite support handled through expanding agent and is supported on supported catalyst
Weight of the mass percentage of Ni, Ni based on the carrier is 18%, and expanding agent is the poly-vinegar acid second that molecular weight is 10000
Alkene, the mass percentage of expanding agent are 3% based on the weight of carrier.
The preparation method of the catalyst of the present embodiment is the following steps are included: polyvinyl acetate is dissolved in ethyl alcohol by (1), with load
Body diatomite unsaturated dipping 3h, dipping temperature in autoclave are 120 DEG C, impregnation pressure 0.3MPa, and sample exists after dipping
At room temperature after aging 2h, 12h is removed in drying in 70 DEG C of baking ovens, then obtains spare carrier in 400 DEG C of Muffle kiln roasting 6.5h,
Muffle furnace heating rate is 2 DEG C/min；(2) nickel nitrate, nickel acetate, nickel sulfate mixing nickel salt are dissolved in deionized water, are adjusted
Solution ph is 2.3；(3) by nickel salt solution and spare carrier, unsaturated dipping 8h, dipping temperature are 50 DEG C in autoclave, leaching
Stain pressure is 1MPa, and sample is at room temperature after aging 2h after dipping, the dry 12h in 70 DEG C of baking ovens, it is dry after sample be placed in 500
Reductase 12 h is in DEG C atmosphere of hydrogen to get C5 hydrogenation of petroleum resin catalyst；
The catalyst performance evaluation method of the present embodiment are as follows: C5 Petropols are dissolved completely in hexamethylene, quality point
Number is 35%, and C5 Petropols material liquid is put into autoclave together with catalyst, is 8MPa, reaction temperature in reaction pressure
Degree reacts 5h under conditions of being 250 DEG C, the quality of the catalyst is the 6% of C5 Petropols quality.
The results are shown in Table 1 for catalyst performance evaluation.
Embodiment 3
The catalyst of the present embodiment comprising the diatomite support handled through expanding agent and is supported on supported catalyst
The mass percentage of Ni, Ni based on the carrier weight be 12%, expanding agent be sodium citrate and PVPK12, expanding agent
Weight of the mass percentage based on carrier is 4%.
The preparation method of the catalyst of the present embodiment the following steps are included: (1) by sodium citrate and PVPK12 be dissolved in from
In sub- water, 5h is impregnated in autoclave unsaturation with carrier diatomaceous earth, dipping temperature is 63 DEG C, impregnation pressure 0.8MPa, dipping
Sample is at room temperature after aging 2h afterwards, and dry 10h, then obtains in 500 DEG C of Muffle kiln roasting 4h spare in 70 DEG C of baking ovens
Carrier, Muffle furnace heating rate are 2 DEG C/min；(2) nickel nitrate, nickel formate, nickel acetate mixing nickel salt are dissolved in deionized water,
Adjusting solution ph is 2.0；(3) nickel salt solution and spare carrier is unsaturated in autoclave to impregnate 8h, dipping temperature 60
DEG C, impregnation pressure 0.6MPa, sample is at room temperature after aging 3h after dipping, the dry 11h in 73 DEG C of baking ovens, it is dry after sample
Reductase 12 .5h is placed in 450 DEG C of atmosphere of hydrogen to get C5 hydrogenation of petroleum resin catalyst；
The catalyst performance evaluation method of the present embodiment are as follows: C5 Petropols are dissolved completely in hexamethylene, quality point
Number is 30%, and C5 Petropols material liquid is put into autoclave together with catalyst, is 7MPa, reaction temperature in reaction pressure
Degree reacts 4.5h under conditions of being 270 DEG C, the quality of the catalyst is the 8% of C5 Petropols quality.
The results are shown in Table 1 for catalyst performance evaluation.
Comparative example 1
The catalyst, method of evaluating performance of the present embodiment are substantially the same manner as Example 3, and unique difference is that the present embodiment is urged
Agent used carrier diatomite does not do expanding treatment.
The results are shown in Table 1 for catalyst performance evaluation.
Comparative example 2
The catalyst performance evaluation method of the present embodiment is substantially the same manner as Example 3, and unique difference is that the present embodiment is urged
Agent is industrial palladium catalyst.
The results are shown in Table 1 for catalyst performance evaluation.
1 catalyst performance evaluation result of table:
| Group | Bromine number/gBr100g-1 | Gardener color number | Softening point/DEG C | Thermal stability |
| Raw material | 22 | 8 | 118.4 | |
| Embodiment 1 | 1.59 | 1 | 97.7 | 3 |
| Embodiment 2 | 0.93 | < 1 (water white) | 100.6 | 2 |
| Embodiment 3 | 0.58 | < 1 (water white) | 98.1 | 1 |
| Comparative example 1 | 13.71 | 4 | 101.8 | 5 |
| Comparative example 2 | 1.16 | 1 | 99.3 | 3 |
As it can be seen from table 1 with use carrier without the catalyst of expanding treatment compared with, and use industrial palladium catalyst
Comparative example 2 is compared, and 3 catalyst of embodiment has better catalytic activity；Expand because reaming can be reduced in C5 hydrogenation of petroleum resin
Resistance is dissipated, improves and is catalyzed utilization rate living, reduce catalyst amount, conducive to the diffusion of reaction heat, reduces catalyst inactivation, and be catalyzed
The nickel particle of agent dispersion is also beneficial to the raising of catalytic activity.
Catalyst stability is investigated using 3 catalyst of embodiment, is urged by the repeat performance of catalyst to evaluate
The stability of agent.Using identical C5 Petropols as raw material, carry out repeating under conditions of reaction condition is with embodiment 3 real
It tests, every completion once adds sampling analysis bromine number after hydrogen, and the results are shown in Table 2.
2 catalyst of table reuses result:
| Number of repetition | Raw material | 1 | 2 | 3 | 4 | 5 |
| Bromine number/gBr100g-1 | 22 | 0.58 | 0.71 | 1.14 | 1.77 | 2.69 |
From table 2 it can be seen that bromine number rises slowly after catalyst is reused 5 times, illustrate that catalyst reuses effect
Good, stability is high, because catalyst after reaming, advantageously reduces inside diffusional resistance, improves the utilization of catalyst active center
Rate is conducive to the diffusion of heat, prevents hot-spot and generates carbon deposit, therefore stability is good.
Above description is the detailed description for the present invention preferably possible embodiments, but embodiment is not limited to this hair
Bright patent claim, it is all the present invention suggested by technical spirit under completed same changes or modifications change, should all belong to
In the covered the scope of the patents of the present invention.
Claims (5)
1. a kind of preparation method of C5 hydrogenation of petroleum resin Raney nickel, the C5 hydrogenation of petroleum resin include with Raney nickel
The diatomite support that handles through expanding agent and it is supported on supported catalyst Ni, the expanding agent is selected from sodium citrate, poly-
One or more of vinylpyrrolidone, polyvinyl acetate, which comprises the following steps: (1) be dissolved in expanding agent
In deionized water or ethyl alcohol, with carrier diatomaceous earth in the autoclave with stirring the unsaturated dipping 3-6h of heating pressurization, after dipping
Sample after aging 2h, dries 7-12h, then in 400-650 DEG C of Muffle kiln roasting at room temperature in 70-100 DEG C of baking oven
3.5-6.5h obtains spare carrier, and Muffle furnace heating rate is 2 DEG C/min；(2) nickel salt is dissolved in deionized water, adjusts solution
PH value is 1.8-2.3；(3) nickel salt solution and spare carrier are heated into the unsaturated dipping 8- of pressurization in the autoclave with stirring
12h, sample is at room temperature after aging 2-4h after dipping, the dry 7-12h in 70-100 DEG C of baking oven, it is dry after sample be placed in 400-
Reductase 12-3h is in 500 DEG C of atmosphere of hydrogen to get C5 hydrogenation of petroleum resin catalyst；Dipping temperature is 50-80 in the step (3)
DEG C, impregnation pressure 0.3-1Mpa.
2. preparation method according to claim 1, which is characterized in that the mass percentage of the expanding agent is based on carrier
Weight be 3-8%.
3. preparation method according to claim 1, which is characterized in that the polyvinylpyrrolidone is selected from PVPK12-
One or more of PVPK30.
4. preparation method according to claim 1, which is characterized in that it is 2000- that the polyvinyl acetate, which is selected from molecular weight,
One or more of 25000 polyvinyl acetate.
5. preparation method according to claim 1, which is characterized in that dipping temperature is 60-120 DEG C in the step (1),
Impregnation pressure is 0.3-2.5MPa.
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|---|---|---|---|---|
| JP2002275212A (en) * | 2001-03-21 | 2002-09-25 | Arakawa Chem Ind Co Ltd | Method for producing hydrogenated petroleum resin and hydrogenation catalyst used for the production method |
| CN101700494A (en) * | 2009-10-22 | 2010-05-05 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst and use thereof |
| CN102924659A (en) * | 2012-11-12 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method for C9 hydrogenation petroleum resin |
| CN103506165A (en) * | 2013-10-11 | 2014-01-15 | 中国海洋石油总公司 | Preparation method of large-aperture fat hydrogenation catalyst |
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2016
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|---|---|---|---|---|
| JP2002275212A (en) * | 2001-03-21 | 2002-09-25 | Arakawa Chem Ind Co Ltd | Method for producing hydrogenated petroleum resin and hydrogenation catalyst used for the production method |
| CN101700494A (en) * | 2009-10-22 | 2010-05-05 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst and use thereof |
| CN102924659A (en) * | 2012-11-12 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method for C9 hydrogenation petroleum resin |
| CN103506165A (en) * | 2013-10-11 | 2014-01-15 | 中国海洋石油总公司 | Preparation method of large-aperture fat hydrogenation catalyst |
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