CN103521230B - Preparation method of unsaturated fat hydrogenation catalyst - Google Patents
Preparation method of unsaturated fat hydrogenation catalyst Download PDFInfo
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- CN103521230B CN103521230B CN201310472517.6A CN201310472517A CN103521230B CN 103521230 B CN103521230 B CN 103521230B CN 201310472517 A CN201310472517 A CN 201310472517A CN 103521230 B CN103521230 B CN 103521230B
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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
Technical field
The present invention relates to Industrial Catalysis technical field.Be specially a kind of preparation method of consaturated oil hydrogenation catalyst; Provide one and first prepare alumina sol carrier in reaction system, then carry out the preparation of catalytic active component and the method for load.
Background technology
Occurring in nature natural oil wide material sources, but contain double bond or triple bond unsaturated bond because of it, be in a liquid state under normal temperature, fusing point is lower more; In addition, under the effect of light, acid-base condition or microorganism, very easily react with the oxygen in air, variable color is spoiled, is difficult to long-term preservation.
Grease lower for these degree of saturation can be become the higher grease of degree of saturation by hydrogenation under certain condition by HYDROGENATION OF OILS AND FATS technique.In this sense, all greases of occurring in nature may be used to hydrogenation.
Reacted by HYDROGENATION OF OILS AND FATS, grease improves fusing point, improves quality, expands purposes, is more conducive to long-term storage and transport, and such grease Catalytic Hydrogenation Techniques arises at the historic moment, and the research of oil hydrogenation catalyst just becomes the emphasis of oil hydrogenation industry concern.
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 all obtain 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 preparation and the load of nickel active catalytic components on this basis again.The catalyst of such preparation can control distribution and the content of active component well, and particle more evenly, more easily disperses, when reacting consaturated oil hydrogenation, activity and selectivity is better.
Summary of the invention
Object of the present invention is exactly on the alumina sol carrier basis of synthesis, carries out preparation and the load of active catalytic components continuously, finally prepares high activity and optionally catalyst.
The present invention is a kind of preparation method of consaturated oil hydrogenation catalyst.It is characterized in that:
First add in a kettle. a certain amount of deionized water, start and stir and be heated to the reaction temperature that specifies, by the aluminum salt solution prepared and alkaline solution with certain speed and stream adds reactor generation alumina sol.After aluminum salt solution all adds, reaction solution pH is regulated with alkaline solution, synthermal lower continuation stirring reaction solution also flows to this solution for continuous the acid solution and alkaline solution that at the uniform velocity add containing nickel salt 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 DEG C dry 3-6 hour cooling, pulverize, 400-600 DEG C pass into nitrogen and hydrogen mixed gas reduction within 3-5 hour, can finished catalyst be obtained.
Described aluminum salt solution is industrial chlorinations aluminium, aluminum nitrate, any one of the acid solution that aluminum sulfate and deionized water are prepared, and also can be the aluminum salt solution that metallic aluminium and acid solution directly prepared any one, in aluminum salt solution, alumina content is 4-15wt%.
One or more in the solution that described alkaline solution is industrial sodium hydroxide, sodium acid carbonate, sodium carbonate, sodium oxalate, sodium acetate and deionized water are mixed with.Concentration is 4-20wt%.
Any one of the solution that the nickel salts such as described nickel salt acidic reagent solution is nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate, nickel acetate, nickel phosphate and deionized water are prepared, also can be any one of the nickel salt solution that metallic nickel and acid solution directly prepared, concentration is 4-30wt%.
First described whole course of reaction needs to prepare alumina sol carrier solution, carries out preparation and the load of nickel active catalytic components on this basis again.
Carry out in the temperature range that described reaction temperature specifies between 60-100 DEG C.The temperature preparing alumina sol can prepare from nickel active catalytic components and the process temperature of load different.
Described filter cake need through several deionization, washing, until in the filter cake of preparation sodium content≤0.1wt%(with Na
2o counts) till, then by filter cake 110-250 DEG C of dry 3-6 hour obtained catalyst precarsor.
The granularity that after described drying, precursor is pulverized is less than 100 orders.
Detailed description of the invention
Embodiment 1
Take 174g solid nitric acid aluminium (Al (NO
3)
39H
2o is placed in 1000ml beaker, adds deionized water, and stirring makes it to dissolve completely and is mixed with the aluminum nitrate solution of salic 5wt%.
Take 108g solid nitric acid nickel (Ni (NO
3)
26H
2o) be placed in 1000ml beaker, add deionized water, stirring makes it to dissolve completely and is mixed with the nickel nitrate solution of 15wt%.
Take 115 solid sodium carbonate (Na
2cO
3) be placed in 2000ml beaker, add deionized water, stirring makes it to dissolve completely and is mixed with the sodium carbonate liquor of 10wt%.
Add a certain amount of deionized water in a kettle., open and stir and be heated to 70 DEG C, also flow with peristaltic pump and at the uniform velocity add aluminum nitrate solution and sodium carbonate liquor, control 0.5 hour reaction time, after aluminum nitrate solution all adds, reaction solution pH to 7.5-8 is regulated with sodium carbonate liquor, continue to this solution and flow at the uniform velocity to add nickel nitrate solution and remaining sodium carbonate liquor, control 0.75 hour reaction time, nickel nitrate solution and sodium carbonate liquor add between rear adjustment reaction solution to pH7-9, continue to stir synthermal aging 0.5 hour, filter, to spend in deionized water to filter cake sodium content≤0.1wt%(with Na
2o counts) till, finally by catalyst precarsor obtained below cooling crush to 100 order after filter cake 250 DEG C of dry 3-6 hours.
Get catalyst precursor powder 1 gram of loading reduction reactor; be warming up to 500 DEG C, pass into nitrogen and hydrogen gas mixture (N2:H2=3:1 volume ratio) and reduce 3-5 hour, cooling; under the protection of nitrogen, the powder after reduction is poured in fixed oil, obtained 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 DEG C, pass into hydrogen, keep reactor pressure to be that 2.0MPa carries out oil hydrogenation reaction.Hydrogenation reaction carries 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 used in the market, and the catalyst nickel content of use is with to prepare sample suitable.
Embodiment 2
Take Al (NO
3)
39H
2o174g, Ni (NO
3)
26H
2o108g, Na
2cO
3115g
Add a certain amount of deionized water in a kettle., open and stir and be heated to 70 DEG C, also flow with peristaltic pump and at the uniform velocity add aluminum nitrate solution and sodium carbonate liquor, control 0.75 hour reaction time, after aluminum nitrate solution all adds, reaction solution pH to 7.5-8 is regulated with sodium carbonate liquor, continue to this solution and flow at the uniform velocity to add nickel nitrate solution and remaining sodium carbonate liquor, control 1 hour reaction time, nickel nitrate solution and sodium carbonate liquor add between rear adjustment reaction solution to pH7-9, continue to stir synthermal aging 0.5 hour, filter, to spend in deionized water to filter cake sodium content≤0.1wt%(with Na
2o counts) till, finally by catalyst precarsor obtained below cooling crush to 100 order after filter cake 250 DEG C of dry 3-6 hours.
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:
Embodiment 3
Take Al (NO
3)
39H
2o174g, Ni (NO
3)
26H
2o108g, Na
2cO
3115g
Add a certain amount of deionized water in a kettle., open and stir and be heated to 80 DEG C, also flow with peristaltic pump and at the uniform velocity add aluminum nitrate solution and sodium carbonate liquor, control 0.75 hour reaction time, after aluminum nitrate solution all adds, reaction solution pH to 7.5-8 is regulated with sodium carbonate liquor, within synthermal aging 0.5 hour, continue to this solution and flow at the uniform velocity to add nickel nitrate solution and remaining sodium carbonate liquor, control 1 hour reaction time, nickel nitrate solution and sodium carbonate liquor add between rear adjustment reaction solution to pH7-9, continue to stir synthermal aging 30 minutes, filter, to spend in deionized water to filter cake sodium content≤0.1wt%(with Na
2o counts) till, finally by catalyst precarsor obtained below cooling crush to 100 order after filter cake 250 DEG C of dry 3-6 hours.
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:
Embodiment 4
Take 128g solid aluminum chloride (AlCl
36H
2o) be placed in 1000ml beaker, add deionized water, stirring makes it to dissolve completely and is mixed with the aluminum nitrate solution of salic 7.5wt%.
Take 90g solid chlorine nickel (NiCl
26H
2o) be placed in 1000ml beaker, add deionized water, stirring makes it to dissolve completely and is mixed with the nickel nitrate solution of 15wt%.
Take 124g solid sodium carbonate (Na
2cO
3) be placed in 2000ml beaker, add deionized water, stirring makes it to dissolve completely and is mixed with the sodium carbonate liquor of 10wt%.
Add a certain amount of deionized water in a kettle., open and stir and be heated to 70 DEG C, also flow with peristaltic pump and at the uniform velocity add liquor alumini chloridi and sodium carbonate liquor, control 0.5 hour reaction time, after liquor alumini chloridi all adds, reaction solution pH to 7.5-8 is regulated with sodium carbonate liquor, continue to this solution and flow at the uniform velocity to add nickel chloride solution and remaining sodium carbonate liquor, control 0.75 hour reaction time, nickel chloride solution and sodium carbonate liquor add between rear adjustment reaction solution to pH7-9, continue to stir synthermal aging 0.5 hour, filter, to spend in deionized water to filter cake sodium content≤0.1wt%(with Na
2o counts) till, finally by catalyst precarsor obtained below cooling crush to 100 order after filter cake 250 DEG C of dry 3-6 hours.
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:
Embodiment 5
Take AlCl
36H
2o128g, NiCl
26H
2o90g, Na
2cO
3124g
Add a certain amount of deionized water in a kettle., open and stir and be heated to 70 DEG C, also flow with peristaltic pump and at the uniform velocity add liquor alumini chloridi and sodium carbonate liquor, control 0.75 hour reaction time, after liquor alumini chloridi all adds, reaction solution pH to 7.5-8 is regulated with sodium carbonate liquor, continue to this solution 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 between rear adjustment reaction solution to pH7-9, continue to stir synthermal aging 0.5 hour, filter, to spend in deionized water to filter cake sodium content≤0.1wt%(with Na
2o counts) till, finally by catalyst precarsor obtained below cooling crush to 100 order after filter cake 250 DEG C of dry 3-6 hours.
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:
Embodiment 6
Take AlCl
36H
2o128g, NiCl
26H
2o90g, Na
2cO
3124g
Add a certain amount of deionized water in a kettle., open and stir and be heated to 75 DEG C, also flow with peristaltic pump and at the uniform velocity add liquor alumini chloridi and sodium carbonate liquor, control 0.75 hour reaction time, after liquor alumini chloridi all adds, reaction solution pH to 7.5-8 is regulated with sodium carbonate liquor, aging reaction solution 0.75 hour, be warming up to 85 DEG C to 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 between rear adjustment reaction solution to pH7-9, continue to stir synthermal aging 0.75 hour, filter, to spend in deionized water to filter cake sodium content≤0.1wt%(with Na
2o counts) till, finally by catalyst precarsor obtained below cooling crush to 100 order after filter cake 250 DEG C of dry 3-6 hours.
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 a certain amount of deionized water is added in a kettle., startup is stirred and is heated to the reaction temperature of regulation, by the aluminum salt solution prepared and alkaline solution with certain speed and stream adds reactor generates alumina sol, after aluminum salt solution all adds, reaction solution pH is regulated with alkaline solution, synthermal lower continuation stirring reaction solution is after 0-1.0 hour, the acid solution and alkaline solution that at the uniform velocity add containing nickel salt is also flowed again to this solution for continuous, reinforced complete aging reaction solution filters for 0.5-1.0 hour, deionized water washing leaching cake, filter cake 110-250 DEG C of cooling in dry 3-6 hour, pulverize, 400-600 DEG C pass into nitrogen and hydrogen mixed gas reduction within 3-5 hour, can finished catalyst be obtained,
Described aluminum salt solution is industrial chlorinations aluminium, aluminum nitrate, any one of the acid solution that aluminum sulfate and deionized water are prepared, or any one of the aluminum salt solution directly prepared for metallic aluminium and acid solution, and in aluminum salt solution, alumina content is 4-15wt%;
One or more in the solution that described alkaline solution is industrial sodium hydroxide, sodium acid carbonate, sodium carbonate, sodium oxalate, sodium acetate and deionized water are mixed with; Concentration is 4-20wt%;
Any one of the solution that the described acid solution containing nickel salt is nickel nitrate, nickelous sulfate, nickel chloride, nickel oxalate, nickel acetate, nickel phosphate nickel salt and deionized water are prepared, or any one of the nickel salt solution directly prepared for metallic nickel and acid solution, concentration is 4-30wt%;
First described whole course of reaction needs to prepare alumina sol carrier solution, carries out preparation and the load of nickel active catalytic components on this basis again;
Carry out in the temperature range that described reaction temperature specifies between 60-100 DEG C, the temperature preparing alumina sol prepare from nickel active catalytic components and the process temperature of load identical or different;
Described filter cake need through several deionization, washing, until with Na in the filter cake of preparation
2till O counts sodium content≤0.1wt%, then by filter cake 110-250 DEG C of dry 3-6 hour obtained catalyst precarsor;
The granularity that after described drying, precursor is pulverized is less than 100 orders.
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| CN104399467B (en) * | 2014-11-10 | 2016-08-24 | 中国海洋石油总公司 | A kind of method preparing oil hydrogenation catalyst at organic-aqueous system |
| 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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| CN101347733A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Nickel-based catalyst |
| CN101306368B (en) * | 2008-07-09 | 2010-06-02 | 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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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161008 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |