CN1229178C - Method for preparing edible grease hydrogenation unit nickel catalyst - Google Patents

Abstract

The present invention provides a method of preparing a unit nickel catalyst for hydrogenating the edible oil. The method adopts SiO2 which is developed by the inventor and has special matter parameters as a carrier; active components of the catalyst are in uniform particle size distribution, and an active center is in uniform density distribution; thus, active selectivity is good, and preparation and performance have favorable repeatability and stability. NiSiO2 catalyst hydrogenation reaction provided by the present invention can be carried out under a lower temperature (below (160 DEG C.) and lower pressure (0.1 to 0.5MPa); an iodine value of unsatisfied edible oil and fat can be reduced from more than 100 to below 1. A double bond part can also be hydrogenated as required so that a melting point of the edible oil and fat can be kept at about 45 DEG C.; a trans-isomer and a double bond migration isomer does not exist in a product so as to accord with the requirements of a food industry.

Description

Edible oil and fat hydrogenation unit Raney nickel preparation method

Technical field: the manufacture method that the present invention relates to the required hydrogenated oil and fat catalyst of food industry.

Technical background:

Edible oil and fat hydrogenation unit Raney nickel, chemical formula can be expressed as Ni/SiO ₂The unit Raney nickel is adopted in edible oil and fat hydrogenation both at home and abroad more, does not generally adopt copper nickel binary catalyst, and the remaining grease deterioration that makes because of trace copper pollutes.External as Japan Patent JP54094489 " NICKEL CATALYST FOROIL AND FAT HYDROGENATION AND ITS USE " (1979), JP54139611 " HYDROGENATION CATALYSTS FOR FATS AND OILS " (1979), European patent EP 259911 " HYDROGENATION CATALYSTS WITH LOW SELECTIVITY TOSOLID FATS " (1988), Deutsche Bundespatent DD145066 " CATALYSTS FOR SELECTIVEHYDROGENATION OF OILS AND FATS " (1980), DD295184 " CATALYSTSFOR HYDROGENATION OF FATS AND OILS " (1991) etc.Domestic CIM catalyst series as developments such as the expensive will of Chengdu Organic Chemistry Inst., Chinese Academy of Sciences bear, CN:1045808A (1990), CN:2050781U (1990), CN:20556257U (1990), CN:2216860Y (1996), CNZL:97205580.0 (1997), CNZL:97205577.0 (1997), CN:1236101A (1999), the Y type high-efficiency grease selective hydrogenation catalyst of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's development etc.

But unit Raney nickel carrier mostly is diatomite both at home and abroad at present, and use SiO is also arranged ₂, but general direct use finished product SiO ₂, not directly preparation.Diatom penus natural materials, bad mechanical strength, easily efflorescence influences the isolated by filtration of catalyst.The SiO for preparing under the diatomite in the different places of production of different batches and the different condition ₂, size distribution, rerum naturas such as pore structure, pore-size distribution, specific area have very big-difference.The load technology of active component Ni in addition, the particle diameter that influences the active component crystallite distributes, the activated centre Density Distribution.The degree of scatter of above-mentioned factor affecting active component, microstructure and macroscopic property influence activity of such catalysts, selectivity after all, and be repeated and stable.And do not appear in the newspapers as yet about the research of the load technology of edible oil and fat unit Raney nickel carrier and active component.

Summary of the invention:

The object of the present invention is to provide a kind of manufacture method of edible oil and fat hydrogenation unit Raney nickel, that wherein adopt is the fixedly SiO of physical parameter that has of inventor oneself development ₂(be equivalent to the carrier in the infusion process as dispersant, list in detail in another patent that the technology of preparing of this carrier is applied at the same time " fatty acid methyl ester hydrogenation catalyst manufacture method and this catalyst carrier technology of preparing "), make this catalyst activity component particle diameter distribution, activated centre Density Distribution be tending towards even, improve activity, the selectivity of unit Raney nickel, make manufacturing and performance have good repeatability and stability, help suitability for industrialized production.

Technical scheme of the present invention is:

With industrial goods Na ₂CO ₃And NiSO ₄7H ₂O is a raw material,

With Na ₂CO ₃And NiSO ₄7H ₂The water that O dissolves in 25-40 part respectively is made into Na ₂CO ₃The aqueous solution and NiSO ₄The aqueous solution, the co-current reactor of packing into;

Selecting fixedly physical parameter for use is that size distribution is that 0.1-0.5 μ m, XRD figure are that a broadening diffraction maximum, BET specific area are arranged about 20 ° is 400-600m at 2 θ angles ²/ g, pore structure are that tubulose pore, the most probable pore-size distribution that two ends are all opened is the SiO of 10-30nm ₂Add in the 50-90 ℃ of water as dispersant, stir and make SiO ₂Suspend, place the co-current reactor below;

Open co-current reactor, with Na ₂CO ₃The aqueous solution and NiSO ₄The aqueous solution while slowly adds, and stirs 60-120min, ageing 6-12h, and suction filtration, wash to there not being SO with 50-90 ℃ distilled water the back ₄ ^2-Use a small amount of absolute ethyl alcohol drip washing again, under 80-150 ℃, dry, grind, sieve, activate, again through 400-550 ℃ of roasting 3-8h, use hydrogen reducing 4-8h, naturally the cooling, promptly make edible oil and fat hydrogenation unit Raney nickel.

In the technique scheme, NiSO ₄7H ₂O, Na ₂CO ₃And SiO ₂Ratio be: Ni: SiO ₂(w/w)=1: 1-4, NiSO ₄7H ₂O: Na ₂CO ₃(w/w)=1: 1-2.

Compared with prior art, the present invention has following advantage:

1, because selected for use good mechanical strength and certain particle to distribute, higher specific surface area has been arranged simultaneously, be suitable for the pore structure of oil hydrogenation reaction and pore size distribution, various physical parameter controlled within the specific limits have a specific rerum natura parameter S iO ₂Make carrier, make with the easier isolated by filtration of the produced catalyst of the inventive method, pollution-free to grease.

2, the Ni/SiO of the inventive method manufacturing ₂On the surfaces externally and internally attached to carrier, the active component particle diameter distributes equably for catalyst, active component, the activated centre Density Distribution is even, active component utilization rate height.

3, the Ni/SiO of the inventive method manufacturing ₂Catalyst is easy isolated by filtration not only, and is active, selectivity is good, and preparation process and hydrogenation performance have good repeatability and stability, more helps suitability for industrialized production.

Ni/SiO with the inventive method manufacturing ₂Catalyst is used for cocounut oil (iodine number 11.26) hydrogenation, and the fixed oil iodine number is about 0.5.

Ni/SiO with the inventive method manufacturing ₂Catalyst is used for soya-bean oil [iodine number 132, refraction index 1.4638 (60 ℃)] hydrogenation, and control catalyst consumption and the time, both hydrogenation fully dropped to below 1 the fixed oil iodine number, and iodine number reduces more than 130; Also but the two keys of reserve part make the soya-bean oil fusing point about 45 ℃.

The Ni/SiO that the inventive method is made ₂Catalyst does not have transisomer and double-bond shift isomers in the product, meet the requirement of food industry.

Specific implementation method:

Get NiSO ₄7H ₂O 36.0g, Na ₂CO ₃17.5g, dissolve in the 500ml water co-current reactor of packing into respectively; Get the SiO that 10g has specific physical parameter ₂Make carrier, add little water and place 50-80 ℃ of stirred in water bath to make SiO ₂Suspend; Open co-current reactor, NiSO ₄And Na ₂CO ₃Solution slowly adds simultaneously, stirs 60-90min; Ageing 8～12h, suction filtration, with the washing of 60-90 ℃ distilled water to there not being SO ₄ ^2-, use a small amount of absolute ethyl alcohol drip washing again, 80-120 ℃ of down oven dry, through grinding, sieves, activating, again at 400-550 ℃ of following roasting 3-8h, with hydrogen (flow 25-30ml/min) reduction 4-8h, get Ni/SiO ₂About catalyst 20g.The noble gas protection is kept in the 40g fixed oil after the cooling down.

Hydrogenation reaction:

400g soya-bean oil (iodine value 132), 0.2-2.0g Ni/SiO ₂Catalyst joins in the 2L reactor in the lump, exhaust or go out air in the still with hydrogen exchange, and temperature is controlled at about 160 ℃, stir speed (S.S.) 800～1000r/min, pressure maintains 0.1-0.8MPa, reaction 60-90min.The soya-bean oil fusing point can maintain about 45 ℃.The product infrared spectrum does not have trans and the double-bond shift isomers.

Claims (2)

1, edible oil and fat hydrogenation unit Raney nickel preparation method is with Na ₂CO ₃, NiSO ₄7H ₂O is that raw material is made, and it is characterized in that:

A. with Na ₂CO ₃And NiSO ₄7H ₂The water that O dissolves in 25-40 part respectively is made into Na ₂CO ₃The aqueous solution and NiSO ₄The aqueous solution, the co-current reactor of packing into;

B. selecting fixedly physical parameter for use is that size distribution is that 0.1-0.5 μ m, XRD figure are that a broadening diffraction maximum, BET specific area are arranged about 20 ° is 400-600m at 2 θ angles ²/ g, pore structure are that tubulose pore, the most probable pore-size distribution that two ends are all opened is the SiO of 10-30nm ₂Add in the 50-90 ℃ of water as dispersant, stir and make SiO ₂Suspend, place the co-current reactor below;

C. open co-current reactor, with Na ₂CO ₃The aqueous solution and NiSO ₄The aqueous solution while slowly adds, and stirs 60-120min, ageing 6-12h, and suction filtration, wash to there not being SO with 50-90 ℃ distilled water the back ₄ ^2-Use a small amount of absolute ethyl alcohol drip washing again, under 80-150 ℃, dry, grind, sieve, activate, again through 400-550 ℃ of roasting 3-8h, use hydrogen reducing 4-8h, naturally the cooling, promptly make edible oil and fat hydrogenation unit Raney nickel.

2, according to the described edible oil and fat hydrogenation unit of claim 1 Raney nickel preparation method, it is characterized in that: NiSO ₄7H ₂O, Na ₂CO ₃And SiO ₂Ratio be: Ni: SiO ₂(w/w)=1: 1-4, NiSO ₄7H ₂O: Na ₂CO ₃(w/w)=1: 1-2.