A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof
[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.