Preparation method of octenal liquid phase hydrogenation catalyst

Abstract

The invention relates to the technical field of catalyst preparation, in particular to a preparation method of an octenal liquid phase hydrogenation catalyst. The method comprises the following steps: 1, preparing a urea solution with a certain concentration; 2, weighing Ni (NO3) 2.6 H2O, Cu (NO3) 2.3 H2O and Mn (NO3) 2.4 H2O according to a certain proportion, and dissolving the Ni (NO3) 2.6 H2O, the Cu (NO3) 2.3 H2O and the Mn (NO3) 2.4 H2O in a urea solution to form a mixed solution; 3, weighing powder SiO2, adding the powder SiO2 into the mixed solution, and continuously stirring; 4, slowly heating the mixed solution to 90-100 DEG C while stirring, and evaporating to dryness to obtain a solid; and 5, drying and roasting the solid to obtain the catalyst precursor. The prepared catalyst can catalyze 2-ethyl hexenal hydrogenation to prepare 2-ethyl hexanol in a high-activity and high-selectivity manner under a mild condition.

Description

Technical field:

[0001] The invention relates to the technical field of catalyst preparation, and in particular to a method for preparing an octenal liquid phase hydrogenation catalyst. Background technology:

[0002] Chinese patents CN105080549A and CN105080549B disclose a catalyst for preparing 2-ethylhexanol by gas phase hydrogenation of octenal and its preparation method. A highly selective octenal hydrogenation catalyst prepared by distributed precipitation is proposed, which solves the problem of easy pulverization of the catalyst during use. The catalyst is mainly composed of 25% to 35% copper oxide, 45% to 60% zinc oxide, 2% to 10% aluminum oxide, 2% to 10% silicon dioxide, and 0.01% to 1% additive. The specific surface area of ​​the catalyst is 30m 2 / g~60m 2 / g, pore volume is 0.17mL / g~0.30mL / g, and average pore radius is 5nm~10nm. The catalyst prepared by the inventive method has high activity and 2-ethylhexanol selectivity, and has better use strength and lower color number, and is suitable for the reaction process of octenal gas phase hydrogenation to 2-ethylhexanol.

[0003] Chinese patent CN114082421A discloses a hydrogenation catalyst and a preparation method thereof and an application thereof in the hydrogenation of isooctylaldehyde. The hydrogenation catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is alumina and / or phosphorus-modified alumina, and the active component is nickel; the specific surface area of ​​the hydrogenation catalyst is 200 to 630 m2 / g, the pore volume is 2 to 4 cm3 / g, and the most probable pore diameter is 10 to 30 nm. The hydrogenation catalyst is applied to the hydrogenation of isooctylaldehyde to isooctylaldehyde and isooctyl alcohol reaction, which can improve the catalytic activity and selectivity.

[0004] Chinese patent CN105854919A discloses a low-temperature hydrogenation catalyst for α,β# unsaturated aldehydes and its preparation method and application. The catalyst described in the present invention is a hexagonal boron nitride-supported precious metal catalyst, which is prepared by impregnating an active precious metal salt on a pretreated carrier and reducing it. Through the fine control and effective combination of carrier pretreatment, impregnation and reduction treatment, the active component can be effectively dispersed on the carrier, and good performance is shown when the content of the precious metal active component is low.

[0005] Chinese patent CN1478596A discloses a process for preparing isooctyl alcohol by hydrogenating a mixture of isooctyl aldehyde and a catalyst used therein, and particularly relates to a process for preparing isooctyl alcohol by liquid phase hydrogenation of a mixture of isooctyl aldehyde and octenol using a novel catalyst and a catalyst used therein. The catalyst uses metal nickel as an active component, alkaline earth metal oxides and / or aluminum oxide as a promoter, and a silicon-containing compound as a carrier. The raw material of the carrier is a porous silicon-containing compound and / or a silicon-containing compound that is viscous in an aqueous solution; the active component nickel is loaded on the carrier in the form of coprecipitation, kneading, or coprecipitation-kneading with the carrier, and is prepared by roasting at 300-800°C. Summary of the invention:

[0006] The technical problem to be solved by the present invention is to provide a method for preparing an octenal liquid phase hydrogenation catalyst, wherein the prepared catalyst can catalyze the hydrogenation of 2-ethylhexenal to 2-ethylhexanol with high activity and high selectivity under mild conditions, thereby overcoming the problems of low activity and selectivity of the existing octenal liquid phase hydrogenation catalyst and high impurity content of the octanol product after hydrogenation.

[0007] The technical solution adopted by the present invention is: a method for preparing an octenal liquid phase hydrogenation catalyst, the method comprising the following steps:

[0008] Step 1: prepare a urea solution of a certain concentration;

[0009] Step 2: Weigh Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, and Mn(NO3)2·4H2O in a certain ratio and dissolve them in urea solution to form a mixed solution;

[0010] Step 3: Weigh powdered SiO2 and add it to the mixed solution while stirring continuously;

[0011] Step 4: slowly heating the mixed solution to 90°C to 100°C while stirring, and evaporating the water to obtain a solid;

[0012] Step 5: The solid material is dried and calcined to obtain a catalyst precursor.

[0013] Furthermore, the concentration of the urea solution in step 1 is 0.05 mol / L to 0.5 mol / L.

[0014] Furthermore, the molar ratio of Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, Mn(NO3)2·4H2O and SiO2 in the mixed solution of step three is x:y:z:6, wherein x+y+6=10, z=0.01-0.20.

[0015] Furthermore, the powdered SiO2 in step three is one or more of white carbon black and pure silicon molecular sieve.

[0016] Furthermore, the solid drying temperature in step 5 is 100°C to 180°C.

[0017] Furthermore, the solid material calcination temperature in step 5 is 400°C to 650°C.

[0018] Furthermore, the reduction activation conditions of the prepared catalyst precursor are: reduction at a constant temperature of 300° C. for 12 hours in a mixed gas with a hydrogen-nitrogen flow rate of 1:50 to 1:0.

[0019] The beneficial effect of the present invention is that the catalyst prepared by the present invention is used for the reaction of preparing octanol by liquid phase hydrogenation of octenal after reduction activation, and has the characteristics of high catalytic hydrogenation activity and high selectivity of product octanol. Description of the drawings:

[0020] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0021] Figure 1 This is the H2-TPR diagram of the catalyst in Example 1. Specific implementation method:

[0022] Comparative Example 1

[0023] Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O were prepared into a solution in a molar ratio of 3:1:0.05, and equal volumes were impregnated on a white carbon black support (the molar ratio of Ni, Cu, Si was 3:1:6). After standing for 24 hours, it was dried in an oven at 120°C and then calcined in a muffle furnace at 500°C to obtain a catalyst precursor X.

[0024] Example 1

[0025] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O to the urea solution in a molar ratio of 3:1:0.05 to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor A.

[0026] Example 2

[0027] Prepare 0.05 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 3:1:0.05 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor B.

[0028] Example 3

[0029] Prepare 0.5 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O to the urea solution in a molar ratio of 3:1:0.05 to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C under stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor C.

[0030] Example 4

[0031] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 4:0:0.05 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 4:0:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor D.

[0032] Example 5

[0033] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O to the urea solution in a molar ratio of 2:2:0.05 to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 2:2:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor E.

[0034] Example 6

[0035] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 1:3:0.05 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 1:3:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor F.

[0036] Example 7

[0037] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 0:4:0.05 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 0:4:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor G.

[0038] Example 8

[0039] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 3:1:0.01 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C under stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain a catalyst precursor H.

[0040] Example 9

[0041] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 3:1:0.10 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor I.

[0042] Example 10

[0043] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 3:1:0.20 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain catalyst precursor J.

[0044] Embodiment 11

[0045] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 3:1:0.05 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution K; slowly heat to 100°C under stirring, evaporate water, dry in an oven at 120°C, and then calcine at 500°C in a muffle furnace to obtain a catalyst precursor K.

[0046] Example 12

[0047] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O to the urea solution in a molar ratio of 3:1:0.05 to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 100°C, and then calcine in a muffle furnace at 400°C to obtain catalyst precursor L.

[0048] Example 13

[0049] Prepare 0.1 mol / L urea solution; add Ni(NO3)2·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a molar ratio of 3:1:0.05 to the urea solution to form a mixed solution; add white carbon black (Ni, Cu, Si molar ratio is 3:1:6) to the mixed solution; slowly heat to 90°C with stirring, evaporate water, dry in an oven at 180°C, and then calcine at 650°C in a muffle furnace to obtain a catalyst precursor M.

[0050] The catalyst precursors prepared in Comparative Example 1 and Examples 1-13 were activated by reduction and then used for the liquid phase hydrogenation of octenal to produce octanol at mild conditions of 120° C. to 130° C. The reaction performance is shown in Table 1.

[0051] Table 1 Octenal liquid phase hydrogenation performance of catalysts

[0052] catalyst Octenal conversion rate (%) Octanol selectivity (%) A 99.9 99.8 B 99.4 99.4 C 96.3 98.9 D 88.9 98.7 E 94.1 99.2 F 91.8 98.7 G 81.6 96.9 H 98.3 99.7 I 99.6 99.6 J 99.1 99.7 K 97.4 98.6 L 99.1 99.0 M 98.4 98.9 X 81.3 95.4

[0053] As shown in Table 1, the catalysts prepared in Examples 1-13 can catalyze the hydrogenation of 2-ethylhexenal to 2-ethylhexanol at a mild condition of 120° C. to 130° C. with high activity and high selectivity.

[0054] It can be understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents to achieve the same technical effects; as long as the use requirements are met, they are within the protection scope of the present invention.

Claims

1. A method for preparing an octenal liquid phase hydrogenation catalyst, characterized in that: The steps of this method are as follows: Step 1: prepare a urea solution of a certain concentration; Step 2: Weigh Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, and Mn(NO3)2·4H2O in a certain ratio and dissolve them in urea solution to form a mixed solution; Step 3: Weigh powdered SiO2 and add it to the mixed solution while stirring continuously; Step 4: slowly heating the mixed solution to 90°C to 100°C while stirring, and evaporating the water to obtain a solid; Step 5: The solid material is dried and calcined to obtain a catalyst precursor.

2. The method for preparing the octenal liquid phase hydrogenation catalyst according to claim 1, wherein: The concentration of the urea solution in step 1 is 0.05 mol / L to 0.5 mol / L.

3. The method for preparing the octenal liquid phase hydrogenation catalyst according to claim 1, wherein: The molar ratio of Ni(NO3)2·6H2O, Cu(NO3)2·3H2O, Mn(NO3)2·4H2O and SiO2 in the mixed solution of step three is x:y:z:6, wherein x+y+6=10, z=0.01-0.

20.

4. The method for preparing the octenal liquid phase hydrogenation catalyst according to claim 1, wherein: The powdered SiO2 in step three is one or more of white carbon black and pure silicon molecular sieve.

5. The method for preparing the octenal liquid phase hydrogenation catalyst according to claim 1, wherein: The solid drying temperature in step 5 is 100°C to 180°C.

6. The method for preparing the octenal liquid phase hydrogenation catalyst according to claim 1, characterized in that: The solid material is calcined at a temperature of 400°C to 650°C in step 5.

7. The method for preparing the octenal liquid phase hydrogenation catalyst according to claim 1, characterized in that: The reduction activation conditions of the prepared catalyst precursor are: reduction at a constant temperature of 300° C. for 12 hours in a mixed gas with a hydrogen-nitrogen flow rate of 1:50 to 1:0.

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