CN104923240A - Sepiolite-loaded nickel-based catalyst modified by two metals, as well as preparation method and application of sepiolite-loaded nickel-based catalyst - Google Patents
Sepiolite-loaded nickel-based catalyst modified by two metals, as well as preparation method and application of sepiolite-loaded nickel-based catalyst Download PDFInfo
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Abstract
The invention relates to sepiolite-loaded nickel-based catalyst modified by two metals of potassium and lanthanum, as well as a preparation method and application of the sepiolite-loaded nickel-based catalyst to adiponitrile hydrogenation. The preparation method comprises the following steps: taking adiponitrile as a raw material and ethanol as a solvent, and taking sepiolite as a carrier of a catalyst to prepare a nickel-based sepiolite-loaded catalyst modified by potassium and lanthanum as additives. The preparation process of the catalyst comprises acid treatment on sepiolite, and steeping, drying, roasting and reducing of sepiolite after acid treatment. During the adiponitrile hydrogenation process, the reaction pressure is 1-2 MPa, and the reaction temperature is 100-120 DEG C. The catalyst has relatively high activity and 6-aminocapronitrile and hexamethylendiamine selectivity under relatively mild reaction conditions, the raw material of sepiolite is cheap and easy to obtain, and low in cost, and the catalyst is simple in preparation method, and has a good application prospect.
Description
Technical field
The present invention relates to a kind of sepiolite supported bimetallic potassium, the nickel-base catalyst of lanthanum modification, its preparation method, and the application in the technique preparing ACN and hexamethylene diamine at adipic dinitrile hydrogenation.
Background technology
Adipic dinitrile hydrogenation mainly generates ACN and hexamethylene diamine, ACN Cyclization caprolactam, and caprolactam is one of important Organic Chemicals, is mainly used to synthetic nylon-6 fiber and nylon-6 engineering plastics.Due to caprolactam have that excellent heat endurance, mechanical strength are high, chemical resistance and machinability, its range of application is quite extensive, is mainly used in the fields such as automobile, medical equipment, boats and ships, electric, articles for daily use.From in the scope in the whole world, the consumer field of caprolactam mainly comprises fiber (civilian silk, industrial yarn, carpet silk), engineering plastics and food package film three major types.In addition, caprolactam can be used for producing 6-aminocaprolc acid (antiplatelet drug), Laurocapram etc. and be worth high chemicals.And hexamethylene diamine is the intermediate preparing nylon-66.Consider according to process condition and economic benefit, the research of adiponitrile partial hydrogenation process has two kinds of selections: one is the catalyst preparing ACN high selectivity, and two is the processes selecting coproduction ACN and hexamethylene diamine.No matter which kind of is selected, and the selective and Hydrogenation of catalyst is all extremely important.In addition, the research also comparative maturity of ACN Cyclization caprolactam process, Rhone-Poulene, Rhodia, BASF and DSM N. V. have all delivered the Patents based on hydrolytic cyclization, no matter be gas phase or liquid phase cyclization process, the productive rate of caprolactam is all considerable, caprolactam selective close to 100%.
About the research of adiponitrile partial hydrogenation, mainly contain vapor phase method and liquid phase method two kinds, the catalyst of bibliographical information, mainly comprises Raney type catalyst, non-loading type nickel-base catalyst, loading type nickel-based catalyst and amorphous alloy catalyst, and metal rhodium is catalyst based etc.In gas phase adiponitrile partial hydrogenation method, different catalyst shows different reaction results.Different Amorphous Ni-P Alloys, Ni-B catalyst application are in the reaction of gas phase adipic dinitrile hydrogenation with chemical preparation for Li etc., and the primary product of reaction is hexamethylene diamine, the selective of amino-capronitrile only has about 30%.The people such as Serra report the application that Ni-MgO catalyst reacts at adiponitrile partial hydrogenation, under very high air speed, achieve when the conversion ratio of adiponitrile is 87% 83% ACN selective.The people such as Medina have investigated the catalyst based performance of the Ni of a series of non-loaded Fe-Ni catalyst and alumina load, and under very high air speed and reaction temperature, the yield of amino nitrile can reach 85%.They have extensively studied additive alkali metal K and carrier α-Al
2o
3the two impact on catalyst performance, thinks: auxiliary agent potassium oxide and carrier α-Al
2o
3jointly improve the reduction activation energy of catalyst precarsor nickel oxide, reduce the reduction degree of NiO, thus suitably limit the activity of catalyst; Potassium forms the Ni active sites of electron rich and the surface alkalinty site of increase catalyst by donations electronics to Ni atom, facilitates the desorption of amino-capronitrile, and then improves the selective of amino-capronitrile; Due to carrier α-Al
2o
3low specific surface area, the sintering that result in the appropriateness of Ni on catalyst surface forms distinctive avtive spot, is also conducive to the formation of ACN.Although in gas phase adiponitrile partial hydrogenation process, it is selective that some research achieves good 6-amino nitrile, and the hydrogen consumption in vapor phase method is very big, reaction temperature is very high, result in higher production cost and more complicated technique.
Liquid phase adiponitrile partial hydrogenation is all mainly the research of the process route around coproduction ACN and hexamethylene diamine.At present, industrial liquid phase adiponitrile partial hydrogenation process be with Raney nickel and Raney cobalt for catalyst, need at very high Hydrogen Vapor Pressure and have a large amount of ammoniacal liquor or alkali hydroxide soln existent condition to carry out.Although the activity of Raney type catalyst is very high, about 70%, there is the shortcomings such as mechanical strength is low, separation difficulty, easily spontaneous combustion, its application be restricted in the yield of ACN due to them.Meanwhile, owing to using buck in a large number, cause equipment corrosion serious, wastewater treatment capacity is large, and reaction pressure is very high, increases production cost further, and economic benefit is not remarkable.
The noble metal catalyst that had researcher the to investigate application in the reaction of liquid phase adiponitrile partial hydrogenation, research shows that the activity of rhodium is best.The people such as Capannelli have prepared Rh/ γ-Al with vapour deposition process
2o
3catalyst, adds a certain amount of sodium hydroxide solution, and under 3MPa and 337K, the conversion ratio of the selective and adiponitrile of amino-capronitrile is respectively 45% and 100%; After raising reaction temperature to 363K, the selective of amino-capronitrile significantly reduces to 5%, mainly defines cycloheximide (selective is 92%).But catalyst circulation once after, inactivation is serious, and amino-capronitrile is selective also significantly to decline; Circulate after twice, although with after ethanol washing again hydrogen treat partly can recover the activity of catalyst, amino-capronitrile selective also very low.The people such as Alini have prepared Rh/ α-Al by ion-exchange
2o
3catalyst application is in the reaction of liquid phase adiponitrile partial hydrogenation, under 3MPa Hydrogen Vapor Pressure, 500psi ammonia pressure, the reaction condition of 100 DEG C, when the conversion ratio of adiponitrile is 60%, the selective of amino-capronitrile reaches 99%, but the recovery utilization rate of noble metal catalyst is low, also easy inactivation, also needs to add a large amount of ammonia or alkali metal hydroxide to suppress the formation of accessory substance simultaneously.
In sum, the above catalyst for adipic dinitrile hydrogenation or be exactly complicated process of preparation, equipment corrosion is serious, or adopts a large amount of noble metals as active component, and easy inactivation, or it is not very high for being exactly activity, makes cost higher like this.Therefore development cost is low, performance is good, and eco-friendly liquid phase adiponitrile partial hydrogenation catalyst has important theory value and application prospect.
Summary of the invention
The object of the present invention is to provide a kind of cost low, economical and effective, universality are strong, environmental friendliness, not etching apparatus and good cycle, can possess higher ACN and hexamethylene diamine optionally catalyst when being applied in adipic dinitrile hydrogenation technique under relatively mild reaction conditions.
Another object of the present invention is to provide a kind of preparation method the preparation method of simple above-mentioned catalyst.
Another object of the present invention is to the application that a kind of above-mentioned catalyst is provided, by by above-mentioned catalyst application in adipic dinitrile hydrogenation technique, catalyst is made to have greater activity and higher ACN and hexamethylene diamine under relatively mild reaction conditions selective, improve working condition, reduce production cost, improve the quality of products.
Technical scheme of the present invention:
A kind of nickel-base catalyst of sepiolite supported bimetallic-modified, this catalyst take sepiolite as carrier, the metallic nickel of supported bi-metallic potassium, lanthanum modification, the load capacity of load component nickel is the 15%-30% of catalyst gross mass, the content of metallic potassium is the 0.5%-1% of catalyst gross mass, and the content of lanthanoid metal is the 2%-3% of catalyst gross mass.
This catalyst is prepared by the following method: by carrier sepiolite at 50-100 DEG C through acid activation process, to filter, washing, dry; Then use the salt solution impregnation of nickel, potassium and lanthanum, filter, dry, grinding, roasting at 300-400 DEG C; Reduce at 350-450 DEG C with hydrogen, cooling obtains catalyst under nitrogen protection.
Preferably be warming up to sintering temperature with the heating rate of 5-10 DEG C/min, be warming up to hydrogen reducing temperature with the heating rate of 4-8 DEG C/min.
Drying after sepiolite acid activation process is preferably carried out at 80-120 DEG C, uses the drying after the salt solution impregnation of nickel, potassium and lanthanum preferably to carry out at 100-120 DEG C.
Working concentration is the hydrochloric acid of 0.5-1.5mol/L, sulfuric acid or salpeter solution carry out acid activation process.
Described catalyst is preferred preparation method comprise the following steps:
1) sepiolite is added in the hydrochloric acid solution of 0.5-1.5moL/L, the solid-liquid mass ratio of sepiolite and hydrochloric acid is 1:10-20, stirs 20-30 hour, be washed with distilled water to neutrality after suction filtration at 50-100 DEG C, dry 1-3 hour at 80-120 DEG C, obtains sour modified meerschaum;
2) by step 1) sour modified meerschaum metallic nickel, potassium and lanthanum metal salt solution dipping 8-12 hour;
3) dry removing maceration extract moisture at 100-120 DEG C of temperature, after the solid abrasive obtained at 300-400 DEG C roasting 2-6 hour;
4) by step 3) roasting after, at 350-450 DEG C, carry out hydrogen reducing 3-5 hour, under nitrogen protection cooling obtain catalyst.
Above-mentioned catalyst application is prepared the technique of ACN and hexamethylene diamine in adipic dinitrile hydrogenation.
The embody rule technique of above-mentioned catalyst is: the technique that described adipic dinitrile hydrogenation prepares ACN and hexamethylene diamine is carried out in the liquid phase, take adiponitrile as raw material, take hydrogen as reducing agent, under solvent and described catalyst existent condition, Hydrogenation is for ACN and hexamethylene diamine, wherein reaction pressure is 1-2MPa, reaction temperature is 100-120 DEG C, and described solvent is absolute ethyl alcohol.
When applying catalyst of the present invention under above-mentioned process conditions, the catalytic effect that can obtain under above-mentioned relatively gentle reaction condition.
The salting liquid of described nickel, potassium and lanthanum is its soluble salt solutions.
The present invention is directed to the complicated process of preparation of the catalyst existence used in adipic dinitrile hydrogenation technique in prior art, or use a large amount of noble metals as active component, equipment easily corrodes, high and active low etc. the present situation of cost, provide a kind of cost low, economical and effective, universality is strong, environmental friendliness, not etching apparatus (without the need to adding a large amount of ammonia or alkali metal hydroxide to suppress the formation of accessory substance), greater activity and higher ACN and hexamethylene diamine optionally catalyst can be had under relatively mild reaction conditions when being applied in adipic dinitrile hydrogenation technique.And the preparation process of this catalyst is simple, the raw material sepiolite used is cheap and easy to get, cost is low, preparation method is simple, there is good application prospect, concrete, in preparation process, by strictly controlling each step and parameter etc., by on sepiolite by the potassium of specific method load certain content, the nickel metal of lanthanum modification, obtain the catalyst of the adipic dinitrile hydrogenation effect that can obtain under mild conditions, and the application of the catalyst that the present invention obtains in adipic dinitrile hydrogenation technique, hinge structure can improve working condition further, reduce production cost, improve the quality of products.
Detailed description of the invention
Following instance is intended to the present invention is described, but the present invention is not limited to following embodiment.
Embodiment 1:
Take the sepiolite of 30 grams, be placed in the single port flask of 1000mL, according to the solid-liquid mass ratio of 1:15, add the hydrochloric acid solution of the 1moL/L of 450mL, put into magneton, be placed in the oil bath pan vigorous stirring 24 hours of constant temperature 75 DEG C, suspension suction filtration, neutrality is put in distilled water washing, and 100 DEG C of dryings obtain required sour modified meerschaum, as carrier after 2 hours.Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o, 0.06474 gram of KNO
3, 0.3115 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, be warming up to 350 DEG C with 6 DEG C/Min heating rate, then roasting 4 hours, obtains K
2o-LaO-NiO/SEP catalyst oxidation state form; after the catalyst of oxidation state form is put into quartz ampoule, tube furnace Program heat up, be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection; carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.5%K-2%La-20%Ni/SEP.
Take 1 gram of above-mentioned 0.5%K-2%La-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 89.56%, and the selective of ACN is 63.15%, and the selective of hexamethylene diamine is 28.32%.
Embodiment 2:
Take 1 gram of above-mentioned 0.5%K-2%La-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 110 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 97.06%, and the selective of ACN is 20.83%, and the selective of hexamethylene diamine is 58.29%.
Embodiment 3:
Take the sepiolite of 30 grams, be placed in the single port flask of 1000mL, according to the solid-liquid mass ratio of 1:15, add the hydrochloric acid solution of the 1moL/L of 450mL, put into magneton, be placed in the oil bath pan vigorous stirring 24 hours of constant temperature 75 DEG C, suspension suction filtration, neutrality is put in distilled water washing, and 100 DEG C of dryings obtain required sour modified meerschaum, as carrier after 2 hours.Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o, 0.09711 gram of KNO
3, 0.3115 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, to heat up at 350 DEG C roasting 4 hours with 6 DEG C/Min heating rate, obtain K
2o-LaO-NiO/SEP catalyst oxidation state form; after the catalyst of oxidation state form is put into quartz ampoule, tube furnace Program heat up, be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection; carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.75%K-2%La-20%Ni/SEP.
Take 1 gram of above-mentioned 0.75%K-2%La-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 88.98%, and the selective of ACN is 70.56%, and the selective of hexamethylene diamine is 19.23%.
Embodiment 4:
Take the sepiolite of 30 grams, be placed in the single port flask of 1000mL, according to the solid-liquid mass ratio of 1:15, add the hydrochloric acid solution of the 1moL/L of 450mL, put into magneton, be placed in the oil bath pan vigorous stirring 24 hours of constant temperature 75 DEG C, suspension suction filtration, neutrality is put in distilled water washing, and 100 DEG C of dryings obtain required sour modified meerschaum, as carrier after 2 hours.Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o, 0.06474 gram of KNO
3, 0.3894 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, be warming up to 350 DEG C with 6 DEG C/Min heating rate, roasting 4 hours.After obtain K
2o-LaO-NiO/SEP catalyst oxidation state form; after the catalyst of oxidation state form is put into quartz ampoule, tube furnace Program heat up, be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection; carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.5%K-2.5%La-20%Ni/SEP.
Take 1 gram of above-mentioned 0.5%K-2.5%La-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 94.37%, and the selective of ACN is 53.26%, and the selective of hexamethylene diamine is 25.24%.
Embodiment 5:
Catalyst in enforcement 1,2 is separated from reaction mixture; after the washing of a small amount of ethanol, 100 DEG C of dryings, heat up at tube furnace Program, be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection; carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain the catalyst composition 0.5%K-2%La-20%Ni/SEP of reducing/regenerating.
Take 1 gram of above-mentioned 0.5%K-2%La-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 88.74%, and the selective of ACN is 62.86%, and the selective of hexamethylene diamine is 27.98%.
Comparative example 1:
Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours; by dried decorating film mortar grind into fine powder; 350 DEG C are warming up to 6 DEG C/Min heating rate; roasting 4 hours, obtains NiO/SEP catalyst oxidation state form, after the catalyst of oxidation state form is put into quartz ampoule; heat up at tube furnace Program; be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection, carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 20%Ni/SEP.
Take 1 gram of above-mentioned 20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 71.46%, and the selective of ACN is 58.22%, and the selective of hexamethylene diamine is 12.28%.
Comparative example 2:
Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o, 0.06474 gram of KNO
3, be placed in the beaker of 50mL, the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, be warming up to 350 DEG C with 6 DEG C/Min heating rate, roasting 4 hours, obtains K
2o-NiO/SEP catalyst oxidation state form, puts into quartz ampoule by the catalyst of oxidation state form, tube furnace Program heat up, be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection, carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.5%K-20%Ni/SEP.
Take 1 gram of above-mentioned 0.5%K-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 75.02%, and the selective of ACN is 65.18%, and the selective of hexamethylene diamine is 19.16%.
Comparative example 3:
Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o, 0.3115 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours; by dried decorating film mortar grind into fine powder; 350 DEG C are warming up to 6 DEG C/Min heating rate; roasting 4 hours, obtains LaO-NiO/SEP catalyst oxidation state form, after the catalyst of oxidation state form is put into quartz ampoule; heat up at tube furnace Program; be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection, carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 2%La-20%Ni/SEP.
Take 1 gram of above-mentioned 2%La-20%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 80.76%, and the selective of ACN is 57.36%, and the selective of hexamethylene diamine is 26.45%.
Comparative example 4:
Take the sepiolite of 30 grams, be placed in the single port flask of 1000mL, according to the solid-liquid mass ratio of 1:15, add the hydrochloric acid solution of the 1moL/L of 450mL, put into magneton, be placed in the oil bath pan vigorous stirring 24 hours of constant temperature 75 DEG C, suspension suction filtration, neutrality is put in distilled water washing, and 100 DEG C of dryings obtain required sour modified meerschaum, as carrier after 2 hours.Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 4.95 grams of Ni (NO
3)
2 .6H
2o, 0.06474 gram of KNO
3, 0.3115 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, be warming up to 300 DEG C with 5 DEG C/Min heating rate, roasting 4 hours, obtains K
2o-LaO-NiO/SEP catalyst oxidation state form; after the catalyst of oxidation state form is put into quartz ampoule, tube furnace Program heat up, be warming up to 250 DEG C with 5 DEG C/Min heating rate under nitrogen protection; carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.5%K-2%La-20%Ni/SEP.
The 0.5%K-2%La-20%Ni/SEP catalyst taking 1 gram of above-mentioned preparation is placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 40.49%, and the selective of ACN is 60.93%, and the selective of hexamethylene diamine is 5.36%.
Comparative example 5:
Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 2.48 grams of Ni (NO
3)
2 .6H
2o, 0.01295 gram of KNO
3, 0.1558 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, be warming up to 350 DEG C with 6 DEG C/Min heating rate, roasting 4 hours, obtains K
2o-LaO-NiO/SEP catalyst oxidation state form; after the catalyst of oxidation state form is put into quartz ampoule, tube furnace Program heat up, be warming up to 400 DEG C with 5 DEG C/Min heating rate under nitrogen protection; carry out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.1%K-1%La-10%Ni/SEP.
Take 1 gram of above-mentioned 0.1%K-1%La-10%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 56.23%, and the selective of ACN is 69.36%, and the selective of hexamethylene diamine is 6.02%.
Comparative example 6:
Take the above-mentioned sour modified meerschaum (SEP) of 5 grams, be placed in the single port flask of 100mL, flood with the distilled water of 25mL, be placed on vigorous stirring in the thermostat water bath of 30 DEG C for subsequent use.Take 2.48 grams of Ni (NO
3)
2 .6H
2o, 0.02589 gram of KNO
3, 0.2336 gram of La (NO
3)
2 .6H
2o is placed in the beaker of 50mL, and the distilled water adding 10mL dissolves.Solution after solution is joined in the sour modified meerschaum suspension of vigorous stirring, stir ageing 10 hours.Suspension after stirring is placed in beaker and puts into drying box 120 DEG C of dryings 12 hours, by dried decorating film mortar grind into fine powder, be warming up to 350 DEG C with 6 DEG C/Min heating rate, roasting 4 hours, obtains K
2o-LaO-NiO/SEP catalyst oxidation state form; after the catalyst of oxidation state form is put into quartz ampoule; heat up at tube furnace Program; first paragraph under nitrogen protection 30-400 DEG C carry out with the intensification of 5 DEG C/Min heating rate; second segment 400-400 DEG C is carried out hydrogen reducing 4 hours, after lower the temperature under nitrogen protection.Obtain catalyst composition: 0.2%K-1.5%La-10%Ni/SEP.
Take 1 gram of above-mentioned 0.2%K-1.5%La-10%Ni/SEP catalyst and be placed in pyroreaction still 100mL liner, add the absolute ethyl alcohol of 50mL, 5 restrain oneself dintrile, put into magneton, sealing autoclave, with air 4 times in nitrogen displacement still, still is evacuated to vacuum by vavuum pump, then reactor is placed in oil bath.When after the 100 DEG C of reaction temperatures being raised to setting, pass into pressurized with hydrogen to 2MPa, open magnetic agitation, reaction timing starts.After reaction, reaction mixture is filtered, the content gas chromatographic analysis of each material in filtrate.The conversion ratio of adiponitrile is 62.01%, and the selective of ACN is 64.72%, and the selective of hexamethylene diamine is 9.03%.
Claims (10)
1. the nickel-base catalyst of a sepiolite supported bimetallic-modified, it is characterized in that, this catalyst take sepiolite as carrier, the metallic nickel of supported bi-metallic potassium, lanthanum modification, the load capacity of load component nickel is the 15%-30% of catalyst gross mass, the content of metallic potassium is the 0.5%-1% of catalyst gross mass, and the content of lanthanoid metal is the 2%-3% of catalyst gross mass.
2. catalyst according to claim 1, is characterized in that, this catalyst is prepared by the following method: by carrier sepiolite at 50-100 DEG C through acid activation process, to filter, washing, dry; Then use the salt solution impregnation of nickel, potassium and lanthanum, filter, dry, grinding, roasting at 300-400 DEG C; Reduce at 350-450 DEG C with hydrogen, cooling obtains catalyst under nitrogen protection.
3. catalyst according to claim 2, is characterized in that, is warming up to sintering temperature with the heating rate of 5-10 DEG C/min, is warming up to hydrogen reducing temperature with the heating rate of 4-8 DEG C/Min.
4. catalyst according to claim 2, is characterized in that, working concentration is the hydrochloric acid of 0.5-1.5mol/L, sulfuric acid or salpeter solution carry out acid activation process.
5. the preparation method of the catalyst described in any one of claim 1-4, is characterized in that, comprises the following steps: by carrier sepiolite at 50-100 DEG C through acid activation process, to filter, washing, dry; Then use the salt solution impregnation of nickel, potassium and lanthanum, filter, dry, grinding, roasting at 300-400 DEG C; Finally reduce at 350-450 DEG C with hydrogen, cooling obtains catalyst under nitrogen protection.
6. preparation method according to claim 5, is characterized in that, is warming up to sintering temperature with the heating rate of 5-10 DEG C/min, is warming up to hydrogen reducing temperature with the heating rate of 4-8 DEG C/min.
7. preparation method according to claim 5, is characterized in that, working concentration is the hydrochloric acid of 0.5-1.5mol/L, sulfuric acid or salpeter solution carry out acid activation process.
8. preparation method according to claim 5, is characterized in that, comprises the following steps:
1) sepiolite is added in the hydrochloric acid solution of 0.5-1.5moL/L, the solid-liquid mass ratio of sepiolite and hydrochloric acid is 1:10-20, stirs 20-30 hour, be washed with distilled water to neutrality after suction filtration at 50-100 DEG C, dry 1-3 hour at 80-120 DEG C, obtains sour modified meerschaum;
2) by step 1) sour modified meerschaum metallic nickel, potassium and lanthanum metal salt solution dipping 8-12 hour;
3) dry removing maceration extract moisture at 100-120 DEG C of temperature, after the solid abrasive obtained at 300-400 DEG C roasting 2-6 hour;
4) in step 3) roasting after, at 350-450 DEG C, carry out hydrogen reducing 3-5 hour, under nitrogen protection cooling obtain catalyst.
9. the catalyst application described in any one of claim 1-4 is prepared the technique of ACN and hexamethylene diamine in adipic dinitrile hydrogenation.
10. application according to claim 9, it is characterized in that, the technique that described adipic dinitrile hydrogenation prepares ACN and hexamethylene diamine is carried out in the liquid phase, take adiponitrile as raw material, take hydrogen as reducing agent, under solvent and described catalyst existent condition, Hydrogenation is for ACN and hexamethylene diamine, and wherein reaction pressure is 1-2MPa, reaction temperature is 100-120 DEG C, and described solvent is absolute ethyl alcohol.
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