CN103521230A - Preparation method of unsaturated fat hydrogenation catalyst - Google Patents

Preparation method of unsaturated fat hydrogenation catalyst Download PDF

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CN103521230A
CN103521230A CN201310472517.6A CN201310472517A CN103521230A CN 103521230 A CN103521230 A CN 103521230A CN 201310472517 A CN201310472517 A CN 201310472517A CN 103521230 A CN103521230 A CN 103521230A
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nickel
preparation
deionized water
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CN103521230B (en
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孙春晖
于海斌
陈永生
刘伟
许岩
刘冬冬
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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Abstract

The invention provides a preparation method of an unsaturated fat hydrogenation catalyst. The method is characterized by comprising the steps of: first preparing a carrier alumina sol with stable performance under certain temperature and stirring effect; then adding a nickel salt-containing acidic solution and an alkaline precipitant into the solution by cocurrent flow; washing and drying the obtained precipitate; and carrying out high temperature reduction to obtain the fat hydrogenation nickel catalyst. The invention has the advantages of simple operation; and the prepared catalyst has good disperse performance and excellent reaction effect when applied to an unsaturated fat hydrogenation reaction.

Description

A kind of preparation method of consaturated oil hydrogenation catalyst
Technical field
The present invention relates to Industrial Catalysis technical field.Be specially a kind of preparation method of consaturated oil hydrogenation catalyst; Provide a kind of and in reaction system, first prepared alumina sol carrier, then carried out the method for preparation the load of catalytic active component.
Background technology
Occurring in nature natural oil wide material sources, but because it contains two keys or triple bond unsaturated bond, under normal temperature, be in a liquid state, 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.
HYDROGENATION OF OILS AND FATS technique can become the lower grease of these degree of saturation into the grease that degree of saturation is higher by hydrogenation under certain condition.In this sense, all greases of occurring in nature may be used to hydrogenation.
By HYDROGENATION OF OILS AND FATS, react, grease has improved fusing point, has improved quality, has expanded purposes, is more conducive to long preservation and transportation, and grease catalytic hydrogenation technology is arisen at the historic moment like this, and the research of oil hydrogenation catalyst just becomes the emphasis that oil hydrogenation industry is paid close attention to.
At present, oil hydrogenation catalyst has one-component metallic catalyst (as Ni, Cu, Pt, Pd etc.), two component metallic catalyst (as Pd/Ag, Pd/Ni etc.), many components metallic catalyst (as Cu-Ni-Co, Cu-Ni-Cr, Cu-Ni-La etc.) and amorphous alloy catalyst (as Ni-P, Ni-B etc.).
Chinese patent CN201110326835, CN201210411738, CN201210417828, CN101554588A have issued the preparation method of oil hydrogenation catalyst.These patents have all obtained good effect in oil hydrogenation reaction.
Advantage of the present invention is that first described whole course of reaction needs to prepare alumina sol carrier solution, carries out on this basis preparation and the load of nickel active catalytic components again.The catalyst of preparation can be controlled distribution and the content of active component well like this, particle more evenly, more easily disperse, when consaturated oil hydrogenation is reacted, activity and selectivity is better.
Summary of the invention
Object of the present invention is exactly on synthetic alumina sol carrier basis, carries out continuously preparation and the load of active catalytic components, finally prepares high activity and catalyst optionally.
The present invention is a kind of preparation method of consaturated oil hydrogenation catalyst.It is characterized in that:
First in reactor, add a certain amount of deionized water, start the reaction temperature that stirs and be heated to regulation, with certain speed stream, add reactor to generate alumina sol the aluminum salt solution preparing and alkaline solution.After aluminum salt solution all adds, with alkaline solution, regulate reaction solution pH, synthermal lower continuation stirring reaction solution at the uniform velocity adds acid solution and the alkaline solution containing nickel salt to this solution for continuous stream after 0-1.0 hour again, reinforced complete aging reaction solution filters for 0.5-1.0 hour, deionized water washing leaching cake, filter cake 110-250 ℃ dry 3-6 hour cooling, pulverize, at 400-600 ℃, pass into nitrogen and hydrogen mixed gas reduction can obtain catalyst finished product in 3-5 hour.
Described aluminum salt solution is industrial aluminium chloride, aluminum nitrate, and any of the acid solution of aluminum sulfate and deionized water preparation, also can be any one of aluminum salt solution that metallic aluminium and acid solution directly prepared, and in aluminum salt solution, alumina content is 4-15wt%.
Described alkaline 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 nickel salt acid reagent solution is any of solution of the nickel salts such as nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate, nickel acetate, nickel phosphate and deionized water preparation, also can be directly any one of nickel salt solution of preparation of metallic nickel and acid solution, concentration is 4-30wt%.
First described whole course of reaction needs to prepare alumina sol carrier solution, carries out on this basis preparation and the load of nickel active catalytic components again.
In the temperature range that described reaction temperature is stipulated between 60-100 ℃, carry out.The temperature of preparing alumina sol can be different from the process temperature of the preparation of nickel active catalytic components and load.
Described filter cake need be through several deionization, washing, until in the filter cake of preparation sodium content≤0.1wt%(with Na 2o meter), till, then filter cake 110-250 ℃ of dry 3-6 hour made to catalyst precarsor.
The granularity that described dry rear precursor is pulverized is less than 100 orders.
The specific embodiment
Embodiment 1
Take 174g solid nitric acid aluminium (Al (NO 3) 39H 2o is placed in 1000ml beaker, adds deionized water, stirs the aluminum nitrate solution that makes it to dissolve completely and be mixed with salic 5wt%.
Take 108g solid nitric acid nickel (Ni (NO 3) 26H 2o) be placed in 1000ml beaker, add deionized water, stir the nickel nitrate solution that makes it to dissolve completely and be mixed with 15wt%.
Take 115 solid sodium carbonate (Na 2cO 3) be placed in 2000ml beaker, add deionized water, stir the sodium carbonate liquor that makes it to dissolve completely and be mixed with 10wt%.
In reactor, add a certain amount of deionized water, open and stir and be heated to 70 ℃, with peristaltic pump stream, at the uniform velocity add aluminum nitrate solution and sodium carbonate liquor, control 0.5 hour reaction time, after aluminum nitrate solution all adds, with sodium carbonate liquor, regulate reaction solution pH to 7.5-8, continuation at the uniform velocity adds nickel nitrate solution and remaining sodium carbonate liquor to this solution stream, control 0.75 hour reaction time, nickel nitrate solution and sodium carbonate liquor add rear adjusting reaction solution between pH7-9, continue to stir synthermal aging 0.5 hour, filter, by deionized water, wash to sodium content≤0.1wt%(in filter cake with Na 2o meter), till, finally cooling crush to 100 order after 250 ℃ of dry 3-6 of filter cake hours is made to catalyst precarsor below.
Get 1 gram of catalyst precursor powder and pack reduction reactor into; be warming up to 500 ℃, pass into nitrogen and hydrogen gas mixture (N2:H2=3:1 volume ratio) reduction 3-5 hour, cooling; under the protection of nitrogen, the powder after reduction is poured in fixed oil, made oil hydrogenation catalyst.
Take the catalyst that 600g palm oil (iodine number is 32) and nickeliferous 0.12g are prepared by said method, pour autoclave into, with nitrogen by after the air displacement in autoclave, open and stir, be warming up to 180 ℃, pass into hydrogen, keeping reactor pressure is that 2.0MPa carries out oil hydrogenation reaction.Hydrogenation reaction is carried out 2 hours altogether, during this period sampling analysis measuring different time sections hydrogenation palm oil iodine number.Control reference sample is the similar industrial catalyst typical sample using in the market, and the catalyst nickel content of use is with to prepare sample suitable.
Figure BDA0000393881400000031
Figure BDA0000393881400000041
Embodiment 2
Take Al (NO 3) 39H 2o174g, Ni (NO 3) 26H 2o108g, Na 2cO 3115g
In reactor, add a certain amount of deionized water, open and stir and be heated to 70 ℃, with peristaltic pump stream, at the uniform velocity add aluminum nitrate solution and sodium carbonate liquor, control 0.75 hour reaction time, after aluminum nitrate solution all adds, with sodium carbonate liquor, regulate reaction solution pH to 7.5-8, continuation at the uniform velocity adds nickel nitrate solution and remaining sodium carbonate liquor to this solution stream, control 1 hour reaction time, nickel nitrate solution and sodium carbonate liquor add rear adjusting reaction solution between pH7-9, continue to stir synthermal aging 0.5 hour, filter, by deionized water, wash to sodium content≤0.1wt%(in filter cake with Na 2o meter), till, finally cooling crush to 100 order after 250 ℃ of dry 3-6 of filter cake hours is made to catalyst precarsor below.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and after hydrogenation, palmitic iodine number is as follows:
Figure BDA0000393881400000042
Embodiment 3
Take Al (NO 3) 39H 2o174g, Ni (NO 3) 26H 2o108g, Na 2cO 3115g
In reactor, add a certain amount of deionized water, open and stir and be heated to 80 ℃, with peristaltic pump stream, at the uniform velocity add aluminum nitrate solution and sodium carbonate liquor, control 0.75 hour reaction time, after aluminum nitrate solution all adds, with sodium carbonate liquor, regulate reaction solution pH to 7.5-8, within synthermal aging 0.5 hour, continue at the uniform velocity to add nickel nitrate solution and remaining sodium carbonate liquor to this solution stream, control 1 hour reaction time, nickel nitrate solution and sodium carbonate liquor add rear adjusting reaction solution between pH7-9, continue to stir synthermal aging 30 minutes, filter, by deionized water, wash to sodium content≤0.1wt%(in filter cake with Na 2o meter), till, finally cooling crush to 100 order after 250 ℃ of dry 3-6 of filter cake hours is made to catalyst precarsor below.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and after hydrogenation, palmitic iodine number is as follows:
Figure BDA0000393881400000051
Embodiment 4
Take 128g solid aluminum chloride (AlCl 36H 2o) be placed in 1000ml beaker, add deionized water, stir the aluminum nitrate solution that makes it to dissolve completely and be mixed with salic 7.5wt%.
Take 90g solid nickel chloride (NiCl 26H 2o) be placed in 1000ml beaker, add deionized water, stir the nickel nitrate solution that makes it to dissolve completely and be mixed with 15wt%.
Take 124g solid sodium carbonate (Na 2cO 3) be placed in 2000ml beaker, add deionized water, stir the sodium carbonate liquor that makes it to dissolve completely and be mixed with 10wt%.
In reactor, add a certain amount of deionized water, open and stir and be heated to 70 ℃, with peristaltic pump stream, at the uniform velocity add liquor alumini chloridi and sodium carbonate liquor, control 0.5 hour reaction time, after liquor alumini chloridi all adds, with sodium carbonate liquor, regulate reaction solution pH to 7.5-8, continuation at the uniform velocity adds nickel chloride solution and remaining sodium carbonate liquor to this solution stream, control 0.75 hour reaction time, nickel chloride solution and sodium carbonate liquor add rear adjusting reaction solution between pH7-9, continue to stir synthermal aging 0.5 hour, filter, by deionized water, wash to sodium content≤0.1wt%(in filter cake with Na 2o meter), till, finally cooling crush to 100 order after 250 ℃ of dry 3-6 of filter cake hours is made to catalyst precarsor below.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and after hydrogenation, palmitic iodine number is as follows:
Figure BDA0000393881400000052
Figure BDA0000393881400000061
Embodiment 5
Take AlCl 36H 2o128g, NiCl 26H 2o90g, Na 2cO 3124g
In reactor, add a certain amount of deionized water, open and stir and be heated to 70 ℃, with peristaltic pump stream, at the uniform velocity add liquor alumini chloridi and sodium carbonate liquor, control 0.75 hour reaction time, after liquor alumini chloridi all adds, with sodium carbonate liquor, regulate reaction solution pH to 7.5-8, continuation at the uniform velocity adds nickel chloride solution and remaining sodium carbonate liquor to this solution stream, control 1 hour reaction time, nickel chloride solution and sodium carbonate liquor add rear adjusting reaction solution between pH7-9, continue to stir synthermal aging 0.5 hour, filter, by deionized water, wash to sodium content≤0.1wt%(in filter cake with Na 2o meter), till, finally cooling crush to 100 order after 250 ℃ of dry 3-6 of filter cake hours is made to catalyst precarsor below.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and after hydrogenation, palmitic iodine number is as follows:
Figure BDA0000393881400000062
Embodiment 6
Take AlCl 36H 2o128g, NiCl 26H 2o90g, Na 2cO 3124g
In reactor, add a certain amount of deionized water, open and stir and be heated to 75 ℃, with peristaltic pump stream, at the uniform velocity add liquor alumini chloridi and sodium carbonate liquor, control 0.75 hour reaction time, after liquor alumini chloridi all adds, with sodium carbonate liquor, regulate reaction solution pH to 7.5-8, aging reaction solution 0.75 hour, be warming up to 85 ℃ and continue and flow at the uniform velocity to add nickel chloride solution and remaining sodium carbonate liquor, control 1 hour reaction time, nickel chloride solution and sodium carbonate liquor add rear adjusting reaction solution between pH7-9, continue to stir synthermal aging 0.75 hour, filter, by deionized water, wash to sodium content≤0.1wt%(in filter cake with Na 2o meter), till, finally cooling crush to 100 order after 250 ℃ of dry 3-6 of filter cake hours is made to catalyst precarsor below.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, palm oil hydroconversion condition are with embodiment 1, and after hydrogenation, palmitic iodine number is as follows:

Claims (1)

1. a preparation method for consaturated oil hydrogenation catalyst, is characterized in that:
First in reactor, add a certain amount of deionized water, start the reaction temperature that stirs and be heated to regulation, with certain speed stream, add reactor to generate alumina sol the aluminum salt solution preparing and alkaline solution, after aluminum salt solution all adds, with alkaline solution, regulate reaction solution pH, synthermal lower continuation stirring reaction solution is after 0-1.0 hour, to this solution for continuous stream, at the uniform velocity add acid solution and the alkaline solution containing nickel salt again, reinforced complete aging reaction solution filters for 0.5-1.0 hour, deionized water washing leaching cake, filter cake 110-250 ℃ dry 3-6 hour cooling, pulverize, at 400-600 ℃, pass into the reduction of nitrogen and hydrogen mixed gas and can obtain catalyst finished product in 3-5 hour,
Described aluminum salt solution is industrial aluminium chloride, aluminum nitrate, and any of the acid solution of aluminum sulfate and deionized water preparation, or be metallic aluminium and any one of the direct aluminum salt solution of preparing of acid solution, in aluminum salt solution, alumina content is 4-15wt%;
Described alkaline 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 nickel salt acid reagent solution is any of solution of nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate, nickel acetate, nickel phosphate nickel salt and deionized water preparation, or be directly any one of nickel salt solution of preparation of metallic nickel and acid solution, concentration is 4-30wt%;
First described whole course of reaction needs to prepare alumina sol carrier solution, carries out on this basis preparation and the load of nickel active catalytic components again;
In the temperature range that described reaction temperature is stipulated between 60-100 ℃, carry out, prepare the temperature of alumina sol or different from the process temperature of nickel active catalytic components preparation and load;
Described filter cake need be through several deionization, washing, until in the filter cake of preparation with Na 2till O meter sodium content≤0.1wt%, then filter cake 110-250 ℃ of dry 3-6 hour made to catalyst precarsor;
The granularity that described dry rear precursor is pulverized is less than 100 orders.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104399467A (en) * 2014-11-10 2015-03-11 中国海洋石油总公司 Method for preparing grease hydrogenation catalyst in organic-aqueous system
CN114058446A (en) * 2021-11-19 2022-02-18 南京师范大学 Preparation of ultrahigh-load two-dimensional nickel-iron catalyst and application of catalyst in preparation of second-generation biodiesel through grease hydrogenation

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Publication number Priority date Publication date Assignee Title
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CN101347733A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Nickel-based catalyst
CN102949996A (en) * 2012-10-26 2013-03-06 中国海洋石油总公司 Preparation method of unsaturated fat nickel hydrogenation catalyst

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CN101306368A (en) * 2008-07-09 2008-11-19 山西大学 Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation
CN102949996A (en) * 2012-10-26 2013-03-06 中国海洋石油总公司 Preparation method of unsaturated fat nickel hydrogenation catalyst

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104399467A (en) * 2014-11-10 2015-03-11 中国海洋石油总公司 Method for preparing grease hydrogenation catalyst in organic-aqueous system
CN114058446A (en) * 2021-11-19 2022-02-18 南京师范大学 Preparation of ultrahigh-load two-dimensional nickel-iron catalyst and application of catalyst in preparation of second-generation biodiesel through grease hydrogenation
CN114058446B (en) * 2021-11-19 2024-01-30 南京师范大学 Preparation of ultra-high-load two-dimensional nickel-iron catalyst and application of catalyst in preparation of second-generation biodiesel by oil hydrogenation

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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No.

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Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd.

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