CN104841436A - Simple preparation method for one-piece high load copper base catalyst - Google Patents
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Abstract
The invention discloses a simple preparation method for a one-piece high load copper base catalyst, which belongs to the technical field of catalyst preparation. Precursors of a metal oxide and active metal are blended at high speed by using a colloid mill, the nucleation process and the crystallization process of precursors of a carrier and an active component are isolated to obtain highly dispersed hydroxide nanoparticle sol, and finally the one-piece high load copper base catalyst which is controllable in metal nucleus diameter and uniform in dispersion is prepared by roasting and reduction. The one-piece high load copper base catalyst is characterized in that nano metal copper is dispersed and anchored in a single magnesium oxide substrate, the specific surface area is 50 to 150 m<2>/g, and the percentage mass content of the copper is 50 to 90 %. After the catalyst is used for hydrogenation preparation of 1, 4-cyclohexanedimethanol by 1, 4-dimethyl cyclohexanedicarboxylic acid and hydrogenation preparation of furfuryl alcohol by furfural, the reaction conversion rate can reach 90 to 99%, and the selectivity to a main product reaches 90 to 99%.
Description
Technical field
The invention belongs to catalyst preparation technical field, in particular, provide a kind of simple integral type high capacity amount copper-based catalysts preparation method, this catalyst is mainly used in the compound hydrogenation containing carbonyl.
Background technology
1,4-cyclohexanedimethanol (CHDM) is being the high dihydroxylic alcohols of a kind of using value, mainly for the production of polyester fiber, also can be used as colloid coating, lamination and note film resin, and this series products has good chemical resistance and Environmental, compared with ethylene glycol, its polyester fiber density of producing is less, lighter, high-melting-point, therefore can bear higher temperature, and its water stability of solution and insulating properties all very good.In addition, the high symmetry of CHDM can also improve crystallinity and the glass transition temperature of mylar; Primary hydroxyl due to CHDM does not have sterically hindered, so just molecule that is easier and raw material acid is close when preparing mylar, in addition, in process of production without the need to adding esterification catalyst, therefore can not introduces impurity, can increase the light transmittance of material.In addition, furfuryl alcohol (FOL), as a kind of important raw material of industry, can be polymerized, alkoxylate, the reactions such as methylolation, can be used for synthesizing furan resin, dyestuff, rubber, rocket dyestuffs etc., in addition all right synthetic fibers, for foundary industry and fine chemicals.
In industrial processes, CHDM can obtained by Isosorbide-5-Nitrae-cyclohexanedicarboxylate (DMCD) hydrogenation.The catalyst that most people adopts is Cu-Cr catalyst, as copper chromite (Eastman Kodak Co.Production of1,4-cyclohexanedimethanol.US, GB 98801211965, Huels Aktiengesellschaft.Method of producingaliphatic and cycloaliphatic diols by catalytic hydrogenation of dicarboxylic acid esters.DE, US5030771.1989), catalyst containing alkaline-earth metal, such as barium is copper chromite catalyst (the Towa KaseiKogyo KK.Production of 1 of co-catalyst, 4-cyclohexanedimethanol.JP 6192146.1992), and (the Arakawa Chem Ind Co Ltd.Production of 1 such as Cu-Cr catalyst containing manganese, 4-cyclohexanedimethanol.JP 6228028.1993).Such as, but Cu-Cr catalyst shortcoming is more, and crushing strength is poor, and the life-span is short, active unstable, not environmentally etc.And under very high condition, just to can carry out hydrogenation reaction, especially pressure, usually at more than 20MPa, suitability for industrialized production will be unfavorable for.
Metal oxide supported metallic catalyst is a kind of common catalyst, and its composition is simple, is widely used in the middle of industrial production.And the metal supported catalyst generally prepared by traditional co-precipitation and infusion process, because Active components distribution is uneven and Support-metal strong interaction is weak, be difficult to prepare the little and finely dispersed carried metal catalysis material of particle diameter, cause metallic particles to reunite in a large number during especially high capacity amount, have a strong impact on hydrogenation activity and the life-span of catalyst.Therefore content of metal can only be controlled in very little scope when this type of metal supported catalyst of preparation, like this compared to high capacity amount catalyst, the quantity in its activated centre will be relatively few a lot, and catalytic performance also can be affected.
For head it off, it is blended that we utilize colloid mill the precursor of metal oxide and active metal to be carried out high speed, by the nucleation process of carrier and active component precursor and crystallization process isolation, finally prepare metal crystal nuclei size tunable, finely dispersed integral type high capacity amount copper-based catalysts, improves performance and the life-span of catalyst.
Summary of the invention
The object of this invention is to provide a kind of simple integral type high capacity amount copper-based catalysts preparation method, this catalyst application is in carbonyls hydrogenation, and such as Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation is for 1,4-CHDM, and furfural hydrogenation prepares furfuryl alcohol.
It is blended that the present invention utilizes colloid mill the precursor of metal oxide and active metal to be carried out high speed, utilize the high dispersive effect that colloid mill High Rotation Speed produces, by the nucleation process of carrier and active component precursor and crystallization process isolation, obtain the hydroxide nanoparticles colloidal sol of high degree of dispersion, metal crystal nuclei size tunable is prepared, finely dispersed integral type high capacity amount copper-based catalysts eventually through roasting and reduction.
The cupper-based catalyst material of MgO-Supported provided by the present invention, does not add any surfactant or uses any template, and a direct step just obtains the integral type copper-based catalysts of high capacity amount and high stability, and specific area is 50 ~ 150m
2/ g, the mass percentage of copper is 50 ~ 90%.
The preparation method of above-mentioned integral type high capacity amount copper-based catalysts is as follows:
A. prepare mixed nitrate solution by soluble nitrate and deionized water, the metal ion in mixed nitrate solution is Cu
2+and Mg
2+, the total concentration of metal ion is 0.8mol/L.The mol ratio of copper ion and magnesium ion is 1 ~ 5.7:1; Wherein Cu
2+molar concentration be 0.38 ~ 0.68mol/L, Mg
2+molar concentration be 0.12 ~ 0.42mol/L.
B. NaOH and soluble inorganic sodium salt are dissolved in deionized water and prepare mixed-alkali solution, described soluble inorganic sodium salt is that nitric acid is received, one in sodium sulphate or sodium chloride.
C. above-mentioned mixing salt solution and mixed-alkali solution equal-volume are poured in colloid mill simultaneously, stir 2 ~ 10 minutes with the rotating speed of 1000-6000 rev/min, isolate sediment, with deionized water centrifuge washing 3 ~ 6 times, then the ratio adding 25ml water in every gram of sediment adds deionized water, in 60 ~ 80 DEG C of crystallization 6 ~ 48 hours, naturally cool to room temperature; Centrifugation, at 60 ~ 100 DEG C, drying obtains copper magnesium double-metal hydroxide precursor for 12 ~ 30 hours;
D. the copper magnesium double-metal hydroxide precursor obtained by step C is placed in Muffle furnace, and with the ramp of 2 ~ 10 DEG C/min to 400-600 DEG C, insulation 3 ~ 12h, naturally cools to room temperature, obtain copper magnesium mixed-metal oxides;
E, the copper magnesium mixed-metal oxides obtained in step D is placed in tube-type atmosphere furnace, be warming up to 200 ~ 400 DEG C with the heating rate of 5 ~ 10 DEG C/min in a hydrogen atmosphere and be incubated 0.5 ~ 5h, after naturally cooling to room temperature, obtaining integral type high capacity amount copper-based catalysts.
The high capacity amount copper base hydrogenation catalyst obtained is characterized, the results are shown in Figure 1 ~ 3.Fig. 1 is the x-ray diffraction pattern (XRD) of product of roasting in embodiment 2, can see the characteristic diffraction peak of CuO and MgO, proves the mixed-metal oxides generated containing copper and magnesium.Fig. 2 reduces the x-ray diffraction pattern (XRD) of gained catalyst in enforcement 2, can find out the characteristic diffraction peak having occurred MgO and Cu simple substance.Fig. 3 is the transmission electron microscope picture (TEM) of enforcement 2 copper-based catalysts, and can find out that metallic copper nano particle is when copper load capacity is up to about 70%, agglomeration, does not appear in its even particle size distribution.
Integral type high capacity amount copper-based catalysts is passed at 210 DEG C the H of 6MPa
2, carry out Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalytic hydrogenation and prepare 1,4-CHDM reaction, reaction conversion ratio can reach 90 ~ 99%, and it can reach 90 ~ 99% to the selective of 1,4-CHDM.By integral type high capacity amount copper-based catalysts at 180 DEG C, under condition of normal pressure, carry out furfural hydrogenation and prepare furfuryl alcohol, conversion ratio can reach 90-99%, and it reaches 90-99% to the selective of furfuryl alcohol.
The present invention has following remarkable result: the integral type high capacity amount copper-based catalysts adopting the present invention to prepare has the advantages that active metal nanoparticles is uniformly dispersed, load capacity is high and avtive spot is many, demonstrates high catalytic hydrogenation activity; Nano-metallic copper dispersion is simultaneously anchored in single magnesia matrix and forms stability and the service life that strong interaction improves catalyst.In addition, technical process of the present invention is to the corrosion-free effect of production equipment, and non-environmental-pollution, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of mixed-metal oxides in embodiment 2.
Fig. 2 is the XRD figure of copper base metal hydrogenation catalyst in embodiment 2.
Fig. 3 is the TEM of copper base hydrogenation catalyst in embodiment 2.
Detailed description of the invention
Embodiment 1
Stoichiometrically precise Cu (NO
3)
26H
2o, Mg (NO
3)
26H
2o deionized water is mixed with mixing salt solution, Cu in solution
2+molar concentration for for 0.5mol/L, Mg
2+molar concentration be 0.3mol/L.NaOH and sodium carbonate are dissolved in deionized water and prepare mixed-alkali solution, wherein NaOH molar concentration is 0.8mol/L, and sodium carbonate molar concentration is 0.4mol/L.Isopyknic 100ml mixing salt solution and mixed-alkali solution are poured in colloid mill simultaneously, the rotating speed of 3000 revs/min stirs 8 minutes, then deionized water centrifuge washing is used 5 times, then to join in 500ml there-necked flask 70 DEG C of crystallization 12 hours together with 250ml water, naturally cool to room temperature afterwards.After filtration, wash, at 60 DEG C, drying obtains hydroxide nanoparticles in 18 hours, then the catalyst precarsor prepared is placed in Muffle furnace, and with the ramp to 600 DEG C of 5 DEG C/min, insulation 3h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate obtained is placed in tube-type atmosphere furnace, is warming up to 300 DEG C in a hydrogen atmosphere and is incubated 3h obtain integral type copper base hydrogenation catalyst with the heating rate of 5 DEG C/min, specific area is 100m
2/ g, the percentage composition of copper is 64%.
Taking 2.0g catalyst utilizes high-pressure hydrogenation reaction to carry out Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation for 1,4-CHDM, and reaction conversion ratio can reach 99.0%, and can reach 96.0% to the conversion ratio of goal response thing 1,4-CHDM.
Embodiment 2
Stoichiometrically precise Cu (NO
3)
26H
2o, Mg (NO
3)
26H
2o, is mixed with mixing salt solution by deionized water, Cu in solution
2+molar concentration for for 0.55mol/L, Mg
2+molar concentration be 0.25mol/L.NaOH and sodium carbonate sodium are dissolved in deionized water and prepare mixed-alkali solution, wherein NaOH molar concentration is 0.90mol/L, and sodium carbonate molar concentration is 0.45mol/L.Isopyknic 100ml mixing salt solution and mixed-alkali solution are poured in colloid mill simultaneously, the rotating speed of 5000 revs/min stirs 6 minutes, then deionized water centrifuge washing is used 4 times, then to join in 500ml there-necked flask 70 DEG C of crystallization 24 hours together with 250ml water, naturally cool to room temperature afterwards.After filtration, wash, at 90 DEG C, drying obtains hydroxide nanoparticles in 30 hours, then the catalyst precarsor prepared is placed in Muffle furnace, and with the ramp to 400 DEG C of 2 DEG C/min, insulation 12h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate obtained is placed in tube-type atmosphere furnace, is warming up to 350 DEG C in a hydrogen atmosphere and is incubated 2h obtain body type copper base hydrogenation catalyst with the heating rate of 10 DEG C/min, specific area is 124m
2/ g, the percentage composition of copper is 73%.
Taking 2.0g catalyst utilizes high-pressure hydrogenation reaction to carry out Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation for 1,4-CHDM, and reaction conversion ratio can reach 98.2%, can reach 98.6% to the conversion ratio of goal response thing 1,4-CHDM.
Embodiment 3
Stoichiometrically precise Cu (NO
3)
26H
2o, Mg (NO
3)
26H
2o, is mixed with mixing salt solution by deionized water, Cu in solution
2+molar concentration be 0.6mol/L, Mg
2+molar concentration be 0.2mol/L.NaOH and sodium carbonate are dissolved in deionized water and prepare mixed-alkali solution, wherein NaOH molar concentration is 1.0mol/L, and sodium carbonate molar concentration is 0.5mol/L.Isopyknic 100ml mixing salt solution and mixed-alkali solution are poured in colloid mill simultaneously, the rotating speed of 6000 revs/min stirs 10 minutes, then deionized water centrifuge washing is used 3 times, then to join in 500ml there-necked flask 80 DEG C of crystallization 48 hours together with 250ml water, naturally cool to room temperature afterwards.After filtration, wash, at 100 DEG C, drying obtains hydroxide nanoparticles in 24 hours, then the catalyst precarsor prepared is placed in Muffle furnace, and with the ramp to 450 DEG C of 5 DEG C/min, insulation 8h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate obtained is placed in tube-type atmosphere furnace, is warming up to 200 DEG C in a hydrogen atmosphere and is incubated 5h obtain body type copper base hydrogenation catalyst with the heating rate of 2 DEG C/min, specific area is 85m
2/ g, the percentage composition of copper is 82%.
Take 2.0g catalyst to utilize high-pressure hydrogenation to react to carry out furfural hydrogenation and prepare furfuryl alcohol, reaction conversion ratio can reach 96.7%, can reach 96.0% to the conversion ratio of goal response thing furfuryl alcohol.
Embodiment 4
Stoichiometrically precise Cu (NO
3)
26H
2o, Mg (NO
3)
26H
2o and Al (NO
3)
39H
2o, is mixed with mixing salt solution by deionized water, Cu in solution
2+molar concentration be 0.4mol/L, Mg
2+molar concentration be 0.4mol/L.NaOH and sodium carbonate are dissolved in deionized water and prepare mixed-alkali solution, wherein NaOH molar concentration is 0.6mol/L, and sodium carbonate molar concentration is 0.3mol/L.Isopyknic 100ml mixing salt solution and mixed-alkali solution are poured in colloid mill simultaneously, the rotating speed of 2000 revs/min stirs 3 minutes, then use deionized water centrifuge washing 6 times, then to join in 500ml there-necked flask 60 DEG C of crystallization 6 hours together with 250ml water, naturally cool to room temperature afterwards.After filtration, wash, at 70 DEG C, drying obtains hydroxide nanoparticles in 24 hours, then the catalyst precarsor prepared is placed in Muffle furnace, and with the ramp to 550 DEG C of 5 DEG C/min, insulation 6h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate obtained is placed in tube-type atmosphere furnace, is warming up to 400 DEG C in a hydrogen atmosphere and is incubated 0.5h obtain body type copper base hydrogenation catalyst with the heating rate of 8 DEG C/min, specific area is 112m
2/ g, the percentage composition of copper is 53%.
Take 2.0g catalyst to utilize high-pressure hydrogenation to react to carry out furfural hydrogenation and prepare furfuryl alcohol, reaction conversion ratio can reach 96.0%, can reach 95.0% to the conversion ratio of goal response thing furfuryl alcohol.
Claims (3)
1. a preparation method for simple integral type high capacity amount copper-based catalysts, it is characterized in that, concrete steps are as follows:
A. prepare mixed nitrate solution by soluble nitrate and deionized water, the metal ion in mixed nitrate solution is Cu
2+and Mg
2+, the total concentration of metal ion is 0.8mol/L; The mol ratio of copper ion and magnesium ion is 1 ~ 5.7:1; Wherein Cu
2+molar concentration be 0.38 ~ 0.68mol/L, Mg
2+molar concentration be 0.12 ~ 0.42mol/L;
B. NaOH and soluble inorganic sodium salt are dissolved in deionized water and prepare mixed-alkali solution, described soluble inorganic sodium salt is that nitric acid is received, one in sodium sulphate or sodium chloride;
C. above-mentioned mixing salt solution and mixed-alkali solution equal-volume are poured in colloid mill simultaneously, stir 2 ~ 10 minutes with the rotating speed of 1000-6000 rev/min, isolate sediment, with deionized water centrifuge washing 3 ~ 6 times, then the ratio adding 25ml water in every gram of sediment adds deionized water, in 60 ~ 80 DEG C of crystallization 6 ~ 48 hours, naturally cool to room temperature; Centrifugation, at 60 ~ 100 DEG C, drying obtains copper magnesium double-metal hydroxide precursor for 12 ~ 30 hours;
D. the copper magnesium double-metal hydroxide precursor obtained by step C is placed in Muffle furnace, and with the ramp of 2 ~ 10 DEG C/min to 400-600 DEG C, insulation 3 ~ 12h, naturally cools to room temperature, obtain copper magnesium mixed-metal oxides;
E, the copper magnesium mixed-metal oxides obtained in step D is placed in tube-type atmosphere furnace, be warming up to 200 ~ 400 DEG C with the heating rate of 5 ~ 10 DEG C/min in a hydrogen atmosphere and be incubated 0.5 ~ 5h, after naturally cooling to room temperature, obtaining integral type high capacity amount copper-based catalysts.
2. a method according to claim 1, is characterized in that, the integral type high capacity amount copper-based catalysts of preparation is that nano-metallic copper dispersion is anchored in single magnesia matrix, and specific area is 50 ~ 150m
2/ g, the mass percentage of copper is 50 ~ 90%.
3. method according to claim 2, is characterized in that, this catalyst application is in Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation for 1,4-CHDM, and furfural hydrogenation prepares furfuryl alcohol.
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| CN109897019A (en) * | 2019-03-27 | 2019-06-18 | 北京林业大学 | A method of preparing furfuryl alcohol by furfural liquid phase hydrogenation is carried out using copper-based catalysts |
| CN110172049A (en) * | 2019-06-28 | 2019-08-27 | 中国科学院大连化学物理研究所 | The method that 5 hydroxymethyl furfural oxidative esterification prepares dehydromucic acid dimethyl ester |
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| CN109897019A (en) * | 2019-03-27 | 2019-06-18 | 北京林业大学 | A method of preparing furfuryl alcohol by furfural liquid phase hydrogenation is carried out using copper-based catalysts |
| CN110172049A (en) * | 2019-06-28 | 2019-08-27 | 中国科学院大连化学物理研究所 | The method that 5 hydroxymethyl furfural oxidative esterification prepares dehydromucic acid dimethyl ester |
| CN113041989A (en) * | 2021-03-19 | 2021-06-29 | 润和催化剂股份有限公司 | Sulfur transfer agent with surface rich in alkaline sites and preparation method thereof |
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Application publication date: 20150819 |