CN102949996A - Preparation method of unsaturated fat nickel hydrogenation catalyst - Google Patents

Abstract

The invention provides a preparation method of an unsaturated fat nickel hydrogenation catalyst. The method is characterized by comprising the steps of: adding a prepared alkaline reagent solution into a reactor; starting to stir and heat; adding a dispersing agent for uniform dissolution; heating the reaction solution to 60-100 DEG C after a certain time; adding an acidic solution containing nickel salt at a certain speed; after feed addition, adding a carrier alumina powder and continuing to stir for 0.5-1.0 h; filtering; washing with deionized water; drying a filter cake at 110-250 DEG C for 3-6 h, cooling and crushing; and introducing a mixed gas of nitrogen and hydrogen at 400-600 DEG C for reduction for 3-5 h, so as to obtain a finished product of the catalyst.

Description

A kind of preparation method of consaturated oil nickel hydrogenation catalyst

Technical field

The present invention relates to the Industrial Catalysis technical field.Be specially a kind of preparation method of consaturated oil nickel hydrogenation catalyst.

Background technology

Natural oil is the grease that directly extracts from the nature animals and plants, and because it contains two keys or triple bond unsaturated bond, so be in a liquid state under the normal temperature, fusing point is lower more; In addition, under the effect of light, acid-base condition or microorganism, very easily react with airborne oxygen, variable color is spoiled, is difficult to long preservation.

In order to improve natural consaturated oil to the stability of oxygen and heat, be convenient to long preservation and the transportation of grease, grease catalytic hydrogenation technology is arisen at the historic moment, and the research of oil hydrogenation catalyst just becomes oil hydrogenation industry outline.At present, oil hydrogenation catalyst has one-component metallic catalyst (such as Ni, Cu, Pt, Pd etc.), two component metallic catalyst (such as Pd/Ag, Pd/Ni etc.), many components metallic catalyst (such as Cu-Ni-Co, Cu-Ni-Cr, Cu-Ni-La etc.) and amorphous alloy catalyst (such as Ni-P, Ni-B etc.).

China Patent No. CN1079503A, CN1944610A, CN102274728A, CN101554588A have issued the preparation method of oil hydrogenation catalyst, from the preparation of active component, catalyst carrier and catalyst breakthrough improvement are arranged all.Although domestic this class research report is a lot, catalyst stability and repeatability all remain further to be investigated.

Advantage of the present invention is to add surfactant to do dispersant when preparation oil hydrogenation catalyst precursor, not only can stop and alleviate the formation of particle hard aggregation, help also to contain that particle " grows up ", make like this catalyst precarsor granularity of preparation less, particle more evenly, more easily disperse, activity and selectivity is better when consaturated oil hydrogenation is reacted.

Summary of the invention

The object of the invention is to by selecting surfactant, make the catalyst precarsor particle of preparation little, even particle size distribution is convenient to catalyst Quick uniform in the oil hydrogenation course of reaction and is disperseed, and discharges the highest activity and selectivity.

The preparation method of a kind of consaturated oil nickel hydrogenation catalyst of the present invention, it is characterized in that: the alkaline reagent solution that at first will prepare in advance adds in the reactor, start and stir and heating, pouring dispersant into fully dissolves evenly it, certain hour afterreaction solution is warming up to 60-100 ℃, the acid solution that will contain nickel salt at the uniform velocity adds with certain speed, after reinforced complete, adding alumina catalyst support powder continues to stir 0.5-1.0 hour, filter, with the deionized water washing, filter cake 110-250 ℃ of cooling in dry 3-6 hour, pulverize, can obtain the catalyst finished product in 3-5 hour 400-600 ℃ of gaseous mixture reduction that passes into nitrogen and hydrogen.

The dispersant of described adding is organic non-ionic surface active agent, be chosen as in Determination of Polyoxyethylene Non-ionic Surfactants, polyoxyethylene polyoxypropylene block type polyethers and the EPE polyol EPE one or more, addition is the 0.1-80wt% of solid alkaline reagent;

Described alkaline reagent solution is one or more in the solution that is mixed with of industrial sodium hydroxide, sodium acid carbonate, sodium carbonate, sodium oxalate, sodium acetate and deionized water; Concentration is 4-20wt%;

Described acid reagent solution is selected from and is any of the solution of the nickel salt of nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate, nickel acetate, nickel phosphate and deionized water preparation, perhaps be directly any one of nickel salt solution of preparation of metallic nickel and acid solution, concentration is 4-30wt%;

Described reaction temperature is carried out in 60-100 ℃ of scope;

Described Washing of Filter Cake number of times is 1-6 time, until the preparation filter cake in Na ₂Till the sodium content≤0.1wt% of O meter, then filter cake 110-250 ℃ made catalyst precarsor in dry 3-6 hour;

The granularity that precursor is pulverized after the described drying is less than 100 orders.

According to preparation method of the present invention, it is characterized in that:

The dispersant addition of described adding is the 2-60wt% of solid alkaline reagent;

Described alkaline reagent solution is selected from one or more in the solution that is mixed with for industrial sodium hydroxide, sodium acid carbonate, sodium carbonate and deionized water; Concentration is 6-18wt%;

Described acid reagent solution is selected from and is any of the solution of the nickel salt of nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate and deionized water preparation, perhaps be direct any of nickel salt solution of preparation of acid solution of metallic nickel and nitric acid, sulfuric acid, hydrochloric acid, concentration is 6-28wt%;

Described reaction temperature is carried out in 70-90 ℃ of scope.

The specific embodiment

Embodiment 1

At first take by weighing 40g solid sodium carbonate (Na ₂CO ₃) place the 1000ml beaker, add deionized water, stirring makes it to dissolve fully and be mixed with the sodium carbonate liquor of 10wt%, then take by weighing 2g Macrogol 2000 (the dispersant addition is the 5wt% of solid sodium carbonate addition) and pour in the sodium carbonate liquor, be stirred to the Macrogol 2000 dissolving evenly.

Take by weighing 108g solid nitric acid nickel (Ni (NO ₃) ₂6H ₂O) place the 800ml beaker, add deionized water, stir the nickel nitrate solution that makes it to dissolve fully and be mixed with 15wt%.

Pour in the reactor preparing the alkaline precipitating agent sodium carbonate liquor that contains the Macrogol 2000 dispersant, open stirring and be heated to 75 ℃, at the uniform velocity add nickel nitrate solution with peristaltic pump, the 1 hour reaction time of control, nickel nitrate solution adds rear conditioned reaction solution between the pH7-9, then adds alumina support, continues to stir synthermal aging 30 minutes, filter, wash to the filter cake sodium content≤0.1wt%(with Na with deionized water ₂The O meter) till, after 250 ℃ of dry 3-6 of filter cake hours, makes catalyst precarsor below cooling crush to 100 order at last.

Get catalyst precursor powder 1 and restrain the reduction reactor of packing into, be warming up to 500 ℃, pass into nitrogen and hydrogen gas mixture (N ₂: H ₂=3:1 volume ratio) reduction is 3-5 hour, cooling, and the powder after will reducing under the protection of nitrogen is poured in the fixed oil, makes oil hydrogenation catalyst.

Take by weighing 530g palm oil (iodine number is 32) and the nickeliferous 0.08gwt% of 4g() by the catalyst of said method preparation, pour autoclave into, with nitrogen with the air displacement in the autoclave after, open and stir, be warming up to 180 ℃, pass into hydrogen, keeping reactor pressure is that 2.0MPa carries out the oil hydrogenation reaction.Hydrogenation reaction was carried out 3 hours altogether, during this period sampling analysis measuring different time sections hydrogenation palm oil iodine number.The control reference sample is the similar industrial catalyst typical sample that uses in the market, and the catalyst nickel content of use is suitable with the preparation sample.

Reaction time (hr)	0	0.5	1	1.5	2	3
							The reference sample iodine number	32	15.74	7.26	2.27	0.81	0.65
Sample 1 iodine number	32	13.74	5.43	1.64	0.77	0.61

Embodiment 2

Take by weighing Na ₂CO ₃40g, Macrogol 2000 4g(dispersant addition are the 10wt% of sodium carbonate addition), Ni (NO ₃) ₂6H ₂O 108g

The preparation method of catalyst is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and palmitic iodine number is as follows behind the hydrogenation:

Reaction time (hr)	0	0.5	1	1.5	2	3
							The reference sample iodine number	32	15.74	7.26	2.27	0.81	0.65
Sample 2 iodine numbers	32	13.51	5.26	1.54	0.65	0.58

Embodiment 3

Take by weighing Na ₂CO ₃40g, Macrogol 4000 2g(dispersant addition are the 5wt% of sodium carbonate addition), NiCl ₂6H ₂O 108g

The preparation method of catalyst is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and palmitic iodine number is as follows behind the hydrogenation:

Reaction time (hr)	0	0.5	1	1.5	2	3
							The reference sample iodine number	32	15.74	7.26	2.27	0.81	0.65
Sample 3 iodine numbers	32	13.56	5.18	1.48	0.58	0.48

Embodiment 4

Take by weighing Na ₂CO ₃40g, Macrogol 4000 4g(dispersant addition are the 10wt% of sodium carbonate addition), NiCl ₂6H ₂O 90g

The preparation method of catalyst is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and the palm oil iodine number is as follows behind the hydrogenation:

Reaction time (hr)	0	0.5	1	1.5	2	3
							The reference sample iodine number	32	15.74	7.26	2.27	0.81	0.65
Sample 4 iodine numbers	32	13.45	5.02	1.35	0.51	0.43

Embodiment 5

Take by weighing Na ₂CO ₃60g, peregal 6g(dispersant addition are the 10wt% of sodium carbonate addition), Ni (NO ₃) ₂6H ₂O 165g

The preparation method of catalyst is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and the palm oil iodine number is as follows behind the hydrogenation:

Reaction time (hr)	0	0.5	1	1.5	2	3
							The reference sample iodine number	32	15.74	7.26	2.27	0.81	0.65
Sample 5 iodine numbers	32	16.14	7.35	2.53	0.89	0.65

Embodiment 6

Take by weighing Na ₂CO ₃60g, peregal 12g(dispersant addition are the 20wt% of sodium carbonate addition), Ni (NO ₃) ₂6H ₂O 165g

The preparation method of catalyst is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and the palm oil iodine number is as follows behind the hydrogenation:

Reaction time (hr)	0	0.5	1	1.5	2	3
							The reference sample iodine number	32	15.74	7.26	2.27	0.81	0.65
Sample 6 iodine numbers	32	15.38	6.18	2.36	0.78	0.59

Claims (2)

1. the preparation method of a consaturated oil nickel hydrogenation catalyst, it is characterized in that: the alkaline reagent solution that at first will prepare in advance adds in the reactor, start and stir and heating, pouring dispersant into fully dissolves evenly it, certain hour afterreaction solution is warming up to 60-100 ℃, the acid solution that will contain nickel salt at the uniform velocity adds with certain speed, after reinforced complete, adding alumina catalyst support powder continues to stir 0.5-1.0 hour, filter, with the deionized water washing, filter cake 110-250 ℃ of cooling in dry 3-6 hour, pulverize, can obtain the catalyst finished product in 3-5 hour 400-600 ℃ of gaseous mixture reduction that passes into nitrogen and hydrogen.

The dispersant of described adding is organic non-ionic surface active agent, be chosen as in Determination of Polyoxyethylene Non-ionic Surfactants, polyoxyethylene polyoxypropylene block type polyethers and the EPE polyol EPE one or more, addition is the 0.1-80wt% of solid alkaline reagent;

Described alkaline reagent solution is one or more in the solution that is mixed with of industrial sodium hydroxide, sodium acid carbonate, sodium carbonate, sodium oxalate, sodium acetate and deionized water; Concentration is 4-20wt%;

Described acid reagent solution is selected from and is any of the solution of the nickel salt of nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate, nickel acetate, nickel phosphate and deionized water preparation, perhaps be directly any one of nickel salt solution of preparation of metallic nickel and acid solution, concentration is 4-30wt%;

Described reaction temperature is carried out in 60-100 ℃ of scope;

Described Washing of Filter Cake number of times is 1-6 time, until the preparation filter cake in Na ₂Till the sodium content≤0.1wt% of O meter, then filter cake 110-250 ℃ made catalyst precarsor in dry 3-6 hour;

The granularity that precursor is pulverized after the described drying is less than 100 orders.

2. according to the described preparation method of claims, it is characterized in that:

The dispersant addition of described adding is the 2-60wt% of solid alkaline reagent;

Described alkaline reagent solution is selected from one or more in the solution that is mixed with for industrial sodium hydroxide, sodium acid carbonate, sodium carbonate and deionized water; Concentration is 6-18wt%;

Described acid reagent solution is selected from and is any of the solution of the nickel salt of nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate and deionized water preparation, perhaps be direct any of nickel salt solution of preparation of acid solution of metallic nickel and nitric acid, sulfuric acid, hydrochloric acid, concentration is 6-28wt%;

Described reaction temperature is carried out in 70-90 ℃ of scope.