CN104399467A - Method for preparing grease hydrogenation catalyst in organic-aqueous system - Google Patents
Method for preparing grease hydrogenation catalyst in organic-aqueous system Download PDFInfo
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Abstract
The invention discloses a method for preparing a grease hydrogenation catalyst in an organic-aqueous system. According to the method, isobutyl acetate and water are employed as mediums for performing a co-precipitation reaction, and then distillation modification is performed, so that the grease hydrogenation catalyst, which employs nickel as an active composition, zirconium, magnesium or iron as an auxiliary agent and aluminium oxide as a carrier, is prepared. Calculated based on the total weight of the catalyst, nickel accounts for 10-30 wt%, the aluminium oxide carrier accounts for 50-85 wt%, and the auxiliary agent zirconium, magnesium or iron accounts for 0.01-10 wt%. The specific surface area of the aluminium oxide carrier is 120-450 cc/g, and the pore volume is 1-2.7 mm/g. The prepared catalyst is high in activity, safe to use and applicable to grease hydrogenation reaction.
Description
Technical field
The present invention relates to oil hydrogenation catalyst technical field, be more particularly adopt organic-aqueous media preparation to be active component with nickel, aluminium oxide is the method with highly active oil hydrogenation catalyst of carrier.
Background technology
The important food source of the mankind is not only by grease, is also the important source material of detergents and cosmetic, rubber plastic, textile printing and dyeing, chemistry painting industry and medical industry.One, a two or more unsaturated bond is all contained in natural grease, Long Term Contact air pole is oxidizable, produces the micromolecular compound such as aldehyde, ketone, acid that peroxide resolves into short carbon chain again, has intense stimulus smell, cause spoiled by rancid oil or fat, be not suitable for using.
Consaturated oil improves the stability of oxygen and heat under the effect of catalyst by hydrogenation, reduce degree of unsaturation, add solid fats content, has both been convenient to store, transport, and which in turn improves the color and luster of grease, fragrance and taste.
At present, the oil hydrogenation catalyst of domestic use is mainly divided into cell cube metallic catalyst, diploid metallic catalyst and triplet metallic catalyst, classify in any case, its main active is all metallic nickel substantially, add other metals a small amount of as auxiliary agent, carrier many employings aluminium oxide, silica, diatomite do skeletal support simultaneously.The work be highly profitable all has been done in CN1415413A, CN101554588A, CN1944610A raising to the preparation of catalyst and activity.
Summary of the invention
Technical problem to be solved by this invention overcomes the problem that prior art catalyst grain size is uneven, reactivity is not high, provides a kind of organic-aqueous system to prepare the method for oil hydrogenation catalyst.
The present invention is a kind of method preparing oil hydrogenation catalyst at organic-aqueous system, it is characterized in that, described oil hydrogenation catalyst take aluminium oxide as carrier, and nickel is active component, and zirconium, magnesium or iron are auxiliary agent; Each component accounts for overall catalyst weight meter, nickel 10-30wt%, alumina support 50-85wt%, auxiliary agent zirconium, magnesium or iron 0.01-10wt%, and described alumina support specific area is 120-450m
2/ g, pore volume is 1-2.7m
3/ g; Wherein said alumina support and catalyst precursor are all synthesize in containing the aqueous solution of isobutyl acetate, then adopt distillation to carry out processing and obtaining; Described method comprises the steps:
1) preparation of the alumina support described in:
Add the i-butyl aqueous solution of ester that a certain amount of deionized water and isobutyl acetate obtain containing 0.1-10wt% in a kettle., 50-95 DEG C is heated under mechanical agitation, add after polyethylene glycol stirs, and stream adds Al2O3 content is the sodium aluminate solution of 100-200g/L and the salpeter solution of 10-30wt%, reaction time controls at 0.5-1 hour, after reaction terminates, reaction solution is regulated to be 7-10 in pH value with ammoniacal liquor, synthermal continuation stirring reaction solution filtered after 0.5-1 hour, absolute ethanol washing filter cake is used again after deionized water washing, after adding isobutyl acetate, distill after adopting high shear homogenous disperse mulser to stir, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of dry 3-8 hour obtain alumina support powder, the weight of wherein said polyethylene glycol is the 0.5wt%-1wt% of deionized water weight, and the volume ratio of described isobutyl acetate and deionized water is 0.5-1,
2) preparation of oil hydrogenation catalyst presoma
The aqueous solution of the isobutyl acetate of preparation containing 0.1-10wt% adds reactor as end water, open and stir and heat, be warming up to 60-95 DEG C, add after polyethylene glycol stirs, zirconium is contained by what prepare in advance, the nickel salt acid solution of Magnesium or iron auxiliary agent and alkaline solution stream joins in end water, after completion of the reaction, add alumina support powder, regulate reaction solution between pH value 7-10 with ammoniacal liquor, continue to stir 0.5-1.5 hour, filter, filter with absolute ethanol washing again after the washing of filter cake deionized water, after adding the isobutyl acetate of 500-1000mL, distill after adopting high shear homogenous disperse mulser to stir, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of dry 3-8 hour obtain the oil hydrogenation catalyst precursor powder loosened, the weight of wherein said polyethylene glycol is the 0.5wt%-1wt% of deionized water weight, and the volume ratio of described isobutyl acetate and deionized water is 0.5-1,
3) oil hydrogenation catalyst presoma reduction
Forged by dried powder 400-600 at a DEG C burning kept 450 DEG C after 3-5 hour and pass into nitrogen, hydrogen mixed gas reduction, cooling, nitrogen protection obtains finished catalyst.
According to said method of the present invention, the described nickeliferous acid solution of oil hydrogenation catalyst of preparing is one or more of the solution prepared of nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate, nickel formate, nickel oxalate and deionized water.
According to said method of the present invention, described oil hydrogenation catalyst alkaline solution of preparing is one or more of the solution prepared of sodium carbonate, sodium acid carbonate, NaOH, sodium oxalate, sodium acetate and deionized water.
The inventive method have employed by the mixed liquor oil-water media system Kaolinite Preparation of Catalyst carrier of isobutyl acetate and water and catalyst precursor, then through distillation process Kaolinite Preparation of Catalyst, obtained catalyst grain size is even, reactivity is high; In addition, the catalyst dispersity that the present invention obtains can be superior, without the need to grinding after drying, decreases preparation section, reduce labour intensity, superior to consaturated oil hydrogenation reactivity worth.
Detailed description of the invention
Embodiment 1
The isobutyl acetate adding 1L deionized water and 100g in a kettle. obtains i-butyl aqueous solution of ester, is heated to 75 DEG C under mechanical agitation, and after the Macrogol 2000 adding 5g stirs, and stream adds 250mL sodium aluminate solution (Al
2o
3content is 200g/L) and the salpeter solution 300mL of 30wt%, reaction time controls at 0.75 hour, after reaction terminates, reaction solution to pH value is regulated to be 8 with ammoniacal liquor, synthermal aging reaction solution filters for 0.75 hour, absolute ethanol washing filter cake is used again after deionized water washing, add and pour round-bottomed flask into after 500mL isobutyl acetate adopts high shear homogenous disperse mulser to stir and distill, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of oven dry obtain alumina support powder.
Take 60g solid nitric acid nickel (Ni (NO
3)
26H
2o) be placed in beaker, add 500g deionized water, stirring makes it to dissolve completely and is mixed with the nickel nitrate solution of 6.7wt%.
16g zirconium nitrate (Zr (NO is added in nickel nitrate solution
3)
45H
2o), stirring makes it fully dissolve.
Take 30g solid sodium carbonate (Na
2cO
3) be placed in beaker, add 500g deionized water, stirring makes it to dissolve completely and is mixed with the sodium carbonate liquor of 5.7wt%.
1L deionized water and 100g isobutyl acetate is added in reactor, open and stir and be heated to 80 DEG C, after adding 5g Macrogol 2000 and stream adds nickel nitrate solution containing zirconium and sodium carbonate liquor, control 1 hour reaction time, after reaction solution all adds, reacting solution pH value to 8 is regulated with ammonia spirit, add the alumina support of preparation, synthermal continuation stirring is filtered for 1 hour, spend deionized water filter cake, 1000mL isobutyl acetate is added again with after ethanol washing leaching cake, pour round-bottomed flask into after using high shear homogenous disperse mulser to stir to distill, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of oven dry obtain catalyst precursor powder.
Get catalyst precursor powder and load reduction reactor, be warming up to that latter 3 hours of 450 DEG C of calcinings are synthermal passes into nitrogen and hydrogen gas mixture reduces 5 hours, cooling nitrogen protection obtains oil hydrogenation catalyst.
Take the catalyst of 1000g tallow oil (iodine number is 36.12) and nickeliferous 0.5g, pour autoclave into, open and stir, be warming up to 185 DEG C, pass into hydrogen, keep reactor pressure to be that 1.5MPa carries out oil hydrogenation reaction.Hydrogenation reaction carries out 2 hours, during this period sampling analysis measuring different time sections hydrogenation tallow oil iodine number.Control reference sample is the similar industrial catalyst typical sample used in the market, and the catalyst nickel content of use is with to prepare sample suitable.Test result is in table 1.
Table 1
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 1 sample iodine number | 36.12 | 21.78 | 10.96 | 3.62 | 2.13 |
Embodiment 2
The isobutyl acetate adding 1L deionized water and 10g in a kettle. obtains i-butyl aqueous solution of ester, is heated to 85 DEG C under mechanical agitation, and after the Macrogol 2000 adding 5g stirs, and stream adds 500mL sodium aluminate solution (Al
2o
3content is 100g/L) and the salpeter solution 600mL of 15wt%, reaction time controls at 1 hour, after reaction terminates, reaction solution to pH value is regulated to be 8 with ammoniacal liquor, synthermal aging reaction solution filters for 0.75 hour, absolute ethanol washing filter cake is used again after deionized water washing, pour round-bottomed flask into after adopting high shear homogenous disperse mulser to stir after adding 500mL isobutyl acetate to distill, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of oven dry obtain alumina support powder.
Take 60g solid nitric acid nickel (Ni (NO
3)
26H
2o), 5g zirconium nitrate (Zr (NO
3)
45H
2o), 0.8g ferric nitrate (Fe (NO
3)
39H
2o).By the nickel nitrate solution of the method preparation iron content of embodiment 1.
Take 25g solid sodium carbonate (Na
2cO
3), by the method preparation sodium carbonate liquor of embodiment 1.
1L deionized water and 100g isobutyl acetate is added in reactor, open and stir and be heated to 95 DEG C, after adding 10g Macrogol 4000, also stream adds containing zirconium, the nickel nitrate solution of iron and sodium carbonate liquor, control 1 hour reaction time, after reaction solution all adds, reacting solution pH value to 9 is regulated with ammonia spirit, add the alumina support of preparation, continue to filter for aging 1 hour, spend deionized water filter cake, 1000mL isobutyl acetate is added again with after ethanol washing leaching cake, pour round-bottomed flask into after using high shear homogenous disperse mulser to stir to distill, until do not have liquid distillate to steam, cooling taking-up 150 DEG C of oven dry obtain catalyst precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with embodiment 1, and after hydrogenation, the iodine number of tallow oil is as shown in table 2:
Table 2
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 2 sample iodine number | 36.12 | 23.57 | 12.11 | 4.34 | 1.51 |
Embodiment 3
Add the isobutyl acetate of 1L deionized water and 5g in a kettle., be heated to 75 DEG C under mechanical agitation, after the Macrogol 4000 adding 5g stirs, and stream adds 500mL sodium aluminate solution (Al
2o
3content is 100g/L) and the salpeter solution 600mL of 15wt%, reaction time controls at 1 hour, after reaction terminates, reaction solution to pH value is regulated to be 7 with ammoniacal liquor, synthermal aging reaction solution filters for 0.75 hour, absolute ethanol washing filter cake is used again after deionized water washing, pour round-bottomed flask into after adopting high shear homogenous disperse mulser to stir after adding 500mL isobutyl acetate to distill, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of oven dry obtain alumina support powder.
Take 60g solid nitric acid nickel (Ni (NO
3)
26H
2o), 0.2g zirconium nitrate (Zr (NO
3)
45H
2o), 0.32g Xiao Suan Magnesium (Mg (NO
3)
26H
2o).The nickel nitrate solution of zirconium, magnesium is contained by the method preparation of embodiment 1.
Take 23g solid sodium carbonate (Na
2cO
3).By the sodium carbonate liquor of the method preparation iron content of embodiment 1.
1L deionized water and 5g isobutyl acetate is added in reactor, open and stir and be heated to 75 DEG C, after adding 5g Macrogol 4000, also stream adds containing zirconium, the nickel nitrate solution of Magnesium and sodium carbonate liquor, control 1 hour reaction time, after reaction solution all adds, reacting solution pH value to 9 is regulated with ammonia spirit, add the alumina support of preparation, continue to filter for aging 1 hour, spend deionized water filter cake, 1000mL isobutyl acetate is added again with after ethanol washing leaching cake, pour round-bottomed flask into after using high shear homogenous disperse mulser to stir to distill, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of oven dry obtain catalyst precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with embodiment 1, and after hydrogenation, the iodine number of tallow oil is as shown in table 3:
Table 3
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 3 sample iodine number | 36.12 | 16.13 | 7.36 | 1.75 | 1.12 |
Embodiment 4
Add the isobutyl acetate of 1L deionized water and 50g in a kettle., be heated to 85 DEG C under mechanical agitation, after the Macrogol 4000 adding 10g stirs, and stream adds 250mL sodium aluminate solution (Al
2o
3content is 200g/L) and the salpeter solution 300mL of 30wt%, reaction time controls at 1 hour, after reaction terminates, reaction solution to pH value is regulated to be 8 with ammoniacal liquor, synthermal aging reaction solution filters for 0.75 hour, absolute ethanol washing filter cake is used again after deionized water washing, pour round-bottomed flask into after adopting high shear homogenous disperse mulser to stir after adding 500mL isobutyl acetate to distill, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of oven dry obtain alumina support powder.
Take 60g solid nitric acid nickel (Ni (NO
3)
26H
2o), 16g zirconium nitrate (Zr (NO
3)
45H
2o).The nickel nitrate solution of zirconium is contained by the method preparation of embodiment 1.
Take 30g solid sodium carbonate (Na
2cO
3).By the method preparation sodium carbonate liquor of embodiment 1.
1L deionized water and 50g isobutyl acetate is added in reactor, open and stir and be heated to 85 DEG C, after adding 10g Macrogol 4000 and stream adds nickel nitrate solution containing zirconium and sodium carbonate liquor, control 1 hour reaction time, after reaction solution all adds, reacting solution pH value to 9 is regulated with ammonia spirit, add the alumina support of preparation, continue to filter for aging 1 hour, spend deionized water filter cake, 1000mL isobutyl acetate is added again with after ethanol washing leaching cake, pour round-bottomed flask into after using high shear homogenous disperse mulser to stir to distill, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of oven dry obtain catalyst precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with embodiment 1, and after hydrogenation, the iodine number of tallow oil is as shown in table 4:
Table 4
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 4 sample iodine number | 36.12 | 19.76 | 10.31 | 3.48 | 1.59 |
Embodiment 5
Add the isobutyl acetate of 1L deionized water and 10g in a kettle., be heated to 75 DEG C under mechanical agitation, after the Macrogol 4000 adding 5g stirs, and stream adds 250mL sodium aluminate solution (Al
2o
3content is 200g/L) and the salpeter solution 300mL of 30wt%, reaction time controls at 1 hour, after reaction terminates, reaction solution to pH value is regulated to be 7 with ammoniacal liquor, synthermal aging reaction solution filters for 0.75 hour, absolute ethanol washing filter cake is used again after deionized water washing, pour round-bottomed flask into after adopting high shear homogenous disperse mulser to stir after adding 500mL isobutyl acetate to distill, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of oven dry obtain alumina support powder.
Take 60g solid nitric acid nickel (Ni (NO
3)
26H
2o), 0.2g zirconium nitrate (Zr (NO
3)
45H
2o), 0.5g ferric nitrate (Fe (NO
3)
39H
2o).The nickel nitrate solution of zirconium, iron is contained by the method preparation of embodiment 1.
Take 17g solid sodium hydroxide (NaOH), by the method preparation sodium carbonate liquor of embodiment 1.
1L deionized water and 10g isobutyl acetate is added in reactor, open and stir and be heated to 85 DEG C, after adding 5g Macrogol 4000, also stream adds containing zirconium, the nickel nitrate solution of iron and sodium hydroxide solution, control 1 hour reaction time, after reaction solution all adds, reacting solution pH value to 7 is regulated with ammonia spirit, add the alumina support of preparation, continue to filter for aging 1 hour, spend deionized water filter cake, 1000mL isobutyl acetate is added again with after ethanol washing leaching cake, pour round-bottomed flask into after using high shear homogenous disperse mulser to stir to distill, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of oven dry obtain catalyst precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with embodiment 1, and after hydrogenation, the iodine number of tallow oil is as shown in table 5:
Table 5
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 5 sample iodine number | 36.12 | 16.57 | 8.25 | 2.18 | 1.43 |
Embodiment 6
The isobutyl acetate adding 1L deionized water and 5g in a kettle. obtains i-butyl aqueous solution of ester, is heated to 85 DEG C under mechanical agitation, and after the Macrogol 4000 adding 5g stirs, and stream adds 500mL sodium aluminate solution (Al
2o
3content is 100g/L) and the salpeter solution 600mL of 15wt%, reaction time controls at 1 hour, after reaction terminates, regulate reacting solution pH value to 7 with ammoniacal liquor, synthermal aging reaction solution filters for 0.75 hour, uses absolute ethanol washing filter cake again after deionized water washing, pour round-bottomed flask into after adopting high shear homogenous disperse mulser to stir after adding 500mL isobutyl acetate to distill, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of oven dry obtain alumina support powder.
Take 54g solid sulphuric acid nickel (NiSO
46H
2o), 0.2g zirconium nitrate (Zr (NO
3)
45H
2o), 0.5g Xiao Suan Magnesium (Mg (NO
3)
26H
2o).The nickel nitrate solution of Gao, Magnesium is contained by the method preparation of embodiment 1.
Take 22g solid sodium carbonate (Na
2cO
3), by the method preparation sodium carbonate nickel nitrate solution of embodiment 1.
1L deionized water and 5g isobutyl acetate is added in reactor, open and stir and be heated to 85 DEG C, after adding 5g Macrogol 4000, also stream adds containing zirconium, the nickel nitrate solution of Magnesium and sodium carbonate liquor, control 1 hour reaction time, after reaction solution all adds, reacting solution pH value to 8 is regulated with ammonia spirit, add the alumina support of preparation, continue to filter for aging 1 hour, spend deionized water filter cake, 1000mL isobutyl acetate is added again with after ethanol washing leaching cake, pour round-bottomed flask into after using high shear homogenous disperse mulser to stir to distill, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of oven dry obtain catalyst precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with embodiment 1, and after hydrogenation, the iodine number of tallow oil is as shown in table 4:
Table 6
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 6 sample iodine number | 36.12 | 16.37 | 8.56 | 2.05 | 1.31 |
Claims (3)
1. organic-aqueous system prepares a method for oil hydrogenation catalyst, it is characterized in that,
Described catalyst take aluminium oxide as carrier, and nickel is active component, and zirconium, magnesium or iron are auxiliary agent; Each component accounts for overall catalyst weight meter, nickel 10-30wt%, alumina support 50-85wt%, auxiliary agent zirconium, magnesium or iron 0.01-10wt%, and described alumina support specific area is 120-450m
2/ g, pore volume is 1-2.7m
3/ g; Wherein said alumina support and catalyst precursor are all synthesize in the aqueous solution of isobutyl acetate, then adopt distillation to carry out processing and obtaining; Described method comprises the steps:
1) preparation of the alumina support described in:
Add the i-butyl aqueous solution of ester that a certain amount of deionized water and isobutyl acetate obtain containing 0.1-10wt% in a kettle., under mechanical agitation, be heated to 50-95 DEG C, add after polyethylene glycol stirs, and stream adds Al
2o
3content is the sodium aluminate solution of 100-200g/L and the salpeter solution of 10-30wt%, reaction time controls at 0.5-1 hour, after reaction terminates, reaction solution is regulated to be 7-10 in pH value with ammoniacal liquor, synthermal continuation stirring reaction solution filtered after 0.5-1 hour, absolute ethanol washing filter cake is used again after deionized water washing, after adding isobutyl acetate, distill after adopting high shear homogenous disperse mulser to stir, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C of dry 3-8 hour obtain alumina support powder; The weight of wherein said polyethylene glycol is the 0.5wt%-1wt% of deionized water weight, and the volume ratio of described isobutyl acetate and deionized water is 0.5-1;
2) preparation of oil hydrogenation catalyst presoma
The aqueous solution of the isobutyl acetate of preparation containing 0.1-10wt% adds reactor as end water, open and stir and heat, be warming up to 60-95 DEG C, add after 0.5-1% polyethylene glycol (taking amount of deionized water as benchmark) stirs, zirconium is contained by what prepare in advance, the nickel salt acid solution of Magnesium or iron auxiliary agent and alkaline solution stream joins in end water, after completion of the reaction, add alumina support powder, regulate reaction solution between pH value 7-10 with ammoniacal liquor, continue to stir 0.5-1.5 hour, filter, filter with absolute ethanol washing again after the washing of filter cake deionized water, after adding the isobutyl acetate of 500-1000mL, distill after adopting high shear homogenous disperse mulser to stir, until do not have liquid distillate to steam, cooling is taken out, 150 DEG C of dry 3-8 hour obtain the oil hydrogenation catalyst precursor powder loosened, the weight of wherein said polyethylene glycol is the 0.5wt%-1wt% of deionized water weight, and the volume ratio of described isobutyl acetate and deionized water is 0.5-1,
3) oil hydrogenation catalyst presoma reduction
Pass into nitrogen, hydrogen mixed gas reduction, cooling at dried powder 400-600 DEG C of calcining was kept 450 DEG C after 3-5 hour, nitrogen protection obtains finished catalyst.
2. according to the method described in claims 1, it is characterized in that, the described nickeliferous acid solution of oil hydrogenation catalyst of preparing is one or more of the solution prepared of nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate, nickel formate, nickel oxalate and deionized water.
3. according to the method described in claims 1, it is characterized in that, described oil hydrogenation catalyst alkaline solution of preparing is one or more of the solution prepared of sodium carbonate, sodium acid carbonate, NaOH, sodium oxalate, sodium acetate and deionized water.
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| CN112691669A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Ni/NiO nano catalyst and preparation method and application thereof |
| CN113070058A (en) * | 2021-03-04 | 2021-07-06 | 青岛创启新能催化科技有限公司 | Composite carrier monoatomic catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
| CN116408088A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Preparation method of nickel hydrogenation catalyst |
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| CN112691669A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Ni/NiO nano catalyst and preparation method and application thereof |
| CN113070058A (en) * | 2021-03-04 | 2021-07-06 | 青岛创启新能催化科技有限公司 | Composite carrier monoatomic catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
| CN113070058B (en) * | 2021-03-04 | 2023-02-28 | 青岛创启新能催化科技有限公司 | Composite carrier single-atom catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
| CN116408088A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Preparation method of nickel hydrogenation catalyst |
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| CN104399467B (en) | 2016-08-24 |
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