Catalyst for hydrogenating isononanal to isononanol, preparation method and application thereof

Abstract

The present invention belongs to the field of aldehyde hydrogenation catalyst preparation, and specifically relates to a catalyst for preparing isononanol by hydrogenation of isononanal, and its preparation method and application. The catalyst includes an active component, a carrier and an auxiliary agent, and the active component: the carrier: the auxiliary agent is 20%-40%: 50%-80%: 1%-10% by mass percentage. Silica sol, aluminum nitrate or aluminum sulfate or aluminum hydroxide, and an alkaline precipitant solution are added to a stirred reactor, and then the nitrate solution of the active component is mixed and added thereto, and then the reaction product is subjected to hydrothermal treatment, and finally washed, filtered, dried, added with auxiliary agents, granulated, roasted, and finally formed into sheets to obtain a catalyst. The isononanal hydrogenation catalyst prepared by the present invention has an isononanal conversion rate of more than 99%, and an isononanol selectivity of more than 98%. It has excellent activity, selectivity and stability, and is conducive to industrial application and promotion.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts for preparing alcohols by hydrogenating aldehydes, and specifically relates to a catalyst for preparing isononanol by hydrogenating isononanal, and a preparation method and application thereof. Background Art

[0002] Isononanol, full name 7-methyl-1-octanol, molecular formula is C9H 20 O, with a relative molecular mass of 144.25, is mainly used to react with phthalic anhydride to produce diisononyl phthalate (DINP), a plasticizer for PVC. As the market gradually recognizes the safety of DINP, the demand for DINP as an environmentally friendly substitute for DOP will grow rapidly, thereby driving the consumption of isononanol to rise rapidly.

[0003] The preparation of isononyl alcohol includes two main steps. The first step is the hydroformylation of octenes to produce isononyl aldehyde, and the second step is the hydrogenation reduction of isononyl aldehyde to produce isononyl alcohol. At present, there are only two isononyl alcohol manufacturers in China, one is Maoming Petrochemical, which cooperates with BASF, and the other is Zibo Qixiang Tengda Chemical Co., Ltd., which cooperates with Exxon, Dow, and Johnson Matthey. All technologies come from foreign countries. In recent years, Chinese researchers have made certain progress in the research on the preparation of high-carbon carbonyl alcohols. The research scope has involved three main catalytic systems for the hydroformylation of high-carbon olefins: homogeneous catalytic system, water / organic two-phase catalytic system, and solid-supported water-phase catalytic system. However, there are few reports in China on the catalyst for hydrogenation of isononyl aldehyde to isononyl alcohol.

[0004] Chinese invention 201911220649.3, a method for preparing isononanol from mixed octenes, the invention mentions a method for preparing 3,5,5-trimethyl-1-hexanol, the isomer of 7-methyl-1-octanol, the aldehyde hydrogenation catalyst used in the invention mainly comprises Ni, Mg and Na as active components, one or more of Co, Ca, Sr and Ba metal elements as auxiliary agents, and one or more of alumina, silica and diatomaceous earth treated with ammonia as carriers.

[0005] Chinese Invention 202010481547.3, a method for preparing isononanol, mentions a 3,5,5-trimethyl-1-hexanal hydrogenation catalyst, and the catalyst used includes one or a mixture of nickel, copper, platinum or palladium.

[0006] Although both invention applications involve the method of hydrogenating 3,5,5-trimethyl-1-hexanal to produce isononanol, this is still different from using 7-methyl-1-octanal as raw material. In addition, the localization of the catalyst for this process as soon as possible will be conducive to the promotion of the catalyst and reduce the price of the catalyst. Summary of the invention

[0007] The purpose of the present invention is to provide a catalyst for preparing isononanol by hydrogenating isononanal, and a preparation method and application thereof.

[0008] The main feature of the present invention is to use one of Cu-Zn alloy, Cu-Zr alloy and Cu-Zn-Zr alloy as the active component, and to prepare the aluminosilicate carrier by gelation and hydrothermal treatment, so that the catalyst can obtain a suitable pore structure and the active components can be dispersed more evenly, giving full play to the synergistic effect of the alloy, thereby improving the activity, selectivity and stability of the catalyst.

[0009] The present invention discloses a catalyst for preparing isononanol by hydrogenating isononanal, and a preparation method and application thereof, which are realized by the following technical scheme: a catalyst for preparing isononanol by hydrogenating isononanal comprises an active component, a carrier and an auxiliary agent, wherein the active component: the carrier: the auxiliary agent are calculated in mass percentages of 20%-40%: 50%-80%: 1%-10%.

[0010] Generally, the active component is one of Cu-Zn alloy, Cu-Zr alloy and Cu-Zn-Zr alloy.

[0011] The molar ratios of the alloy are Cu:Zn=1:1-2.5, Cu-Zr=1:0.5-1, Cu:Zn:Zr=1:0.5-1.5:0.5-1.

[0012] The carrier used is aluminosilicate, wherein the molar ratio of SiO2:Al2O3 is 4-1:1.

[0013] The auxiliary agent is selected from at least one of potassium oxide, magnesium oxide and lanthanum oxide.

[0014] The present invention also relates to a method for preparing the catalyst, comprising the following steps:

[0015] 1) Add silica sol, aluminum nitrate or aluminum sulfate or aluminum hydroxide, and alkaline precipitant solution into a stirred reactor, and react at 60-90° C. for 20-40 minutes;

[0016] 2) Mix the nitrate solution of the active component and slowly add it to the reactor in step 1), controlling the reaction time to 20-40 min;

[0017] 3) placing the catalyst precursor obtained in step 2) into a stirred autoclave and subjecting it to hydrothermal treatment at 120-160° C. for 2-8 h;

[0018] 4) The product in step 3) is washed, filtered, dried, added with an auxiliary agent, granulated, roasted, and finally water and graphite are added to form tablets.

[0019] Generally, the alkaline precipitant is one of NaOH, KOH, Na2CO3, and K2CO3.

[0020] The calcination temperature is 350° C.-400° C., and the calcination time is 2-4 hours.

[0021] The invention also relates to the application of the catalyst, which can be used for aldehyde hydrogenation reaction.

[0022] When the catalyst is used for the reaction of hydrogenating isononanal to produce isononanol, the reaction temperature is 120-250° C. and the reaction pressure is 3-4 MPa.

[0023] Beneficial effects:

[0024] (1) The present invention uses one of Cu-Zn alloy, Cu-Zr alloy and Cu-Zn-Zr alloy as the active component, which can give full play to the synergistic effect of the active components and improve the activity of the catalyst;

[0025] (2) The present invention adopts a self-made aluminosilicate method to promote the dispersion of the carrier and the active component, improve the activity of the carrier, and enhance the selectivity of the catalyst;

[0026] (3) The technical method adopted by the present invention is simple, conducive to industrial application and promotion, and has important social and economic significance. DETAILED DESCRIPTION

[0027] The following examples are only used to further explain the content and effects of the present invention, rather than to limit the present invention.

[0028] Example 1

[0029] The molar ratio of SiO2:Al2O3 is 4:1. 552g of 40% silica sol, 405.9g of aluminum nitrate nonahydrate, and 200g of NaOH are weighed and dissolved in 3L of deionized water to prepare a solution, which is added to a stirred reactor and reacted at 70°C for 30min; according to the molar ratio of Cu:Zn=1:1, 187.56g of Cu(NO3)2 and 189.4g of Zn(NO3)2 are weighed and dissolved in 1L of deionized water to prepare a mixed solution; the mixed solution is added to the reactor and the reaction time is controlled to 30min; the obtained catalyst precursor is placed in a stirred pressure autoclave and hydrothermally treated at 140°C for 6h; the product is poured out, washed, filtered, dried, 23g of potassium oxide additive is added, granulated, and calcined at 360°C for 4h, and finally water and graphite are added to form tablets to obtain catalyst C1.

[0030] Example 2

[0031] The molar ratio of SiO2:Al2O3 is 3:1. 653.3g of 40% silica sol, 292.3g of aluminum sulfate, and 160g of NaOH are weighed and dissolved in 2.5L of deionized water to prepare a solution, which is added to a stirred reactor and reacted at 60°C for 40min. According to the molar ratio of Cu:Zr=1:1, 187.56g of Cu(NO3)2 and 29.3g of Zr(NO3)2·5H2O4 are weighed and dissolved in 1L of deionized water to prepare a mixed solution. The mixed solution is added to the reactor and the reaction time is controlled to 20min. The obtained catalyst precursor is placed in a stirred pressure autoclave and hydrothermally treated at 120°C for 4h. The product is poured out, washed, filtered, and dried, 29g of magnesium oxide additive is added, granulated, and calcined at 400°C for 2h. Finally, water and graphite are added to form tablets to obtain catalyst C2.

[0032] Example 3

[0033] The molar ratio of SiO2:Al2O3 is 2:1. 525g of 40% silica sol, 273g of aluminum hydroxide, and 406g of KOH are weighed, dissolved in 4.5L of deionized water to form a solution, added to a stirred reactor, and reacted at 80°C for 20min; according to the molar ratio of Cu:Zn=1:2.5, 187.56g of Cu(NO3)2 and 473.5g of Zn(NO3)2 are weighed and dissolved in 2L of deionized water to form a mixed solution; the mixed solution is added to the reactor, and the reaction time is controlled to 40min; the obtained catalyst precursor is placed in a stirred pressure autoclave, and hydrothermally treated at 160°C for 2h; the product is poured out, washed, filtered, and dried, 35.3g of lanthanum oxide additive is added, granulated, and calcined at 380°C for 2h, and finally water and graphite are added to form tablets to obtain catalyst C3.

[0034] Example 4

[0035] The molar ratio of SiO2:Al2O3 is 1:1. 525g of 40% silica sol, 546g of aluminum hydroxide, and 159g of Na2CO3 are weighed and dissolved in 1L of deionized water to prepare a solution, which is added to a stirred reactor and reacted at 90°C for 20min. According to the molar ratio of Cu:Zr=1:0.5, 187.56g of Cu(NO3)2 and 14.7g of Zr(NO3)2·5H2O2 are weighed and dissolved in 2L of deionized water to prepare a mixed solution. The mixed solution is added to the reactor and the reaction time is controlled to 40min. The obtained catalyst precursor is placed in a stirred pressure autoclave and hydrothermally treated at 120°C for 8h. The product is poured out, washed, filtered, dried, granulated, and calcined at 350°C for 4h. Finally, water and graphite are added to form tablets to obtain catalyst C4.

[0036] Example 5

[0037] SiO2:Al2O3 molar ratio of 3:1 Weigh 793g of 40% silica sol, 1322g of aluminum nitrate nonahydrate, and 276g of K2CO3, dissolve in 2L of deionized water to prepare a solution, add it into a stirred reactor, and react at 60°C for 30min; according to the molar ratio of Cu:Zn:Zr = 1:0.5:0.5, weigh Cu(NO3)2187.56g, Zn(NO3)294.7g, Zr( NO3)2·5H2O214.7g was dissolved in 2L of deionized water to prepare a mixed solution; the mixed solution was added into a reactor and the reaction time was controlled to be 40min; the obtained catalyst precursor was placed in a pressure autoclave with stirring and hydrothermally treated at 160°C for 4h; the product was poured out, washed, filtered, and dried, 71g of magnesium oxide additive was added, granulated, and calcined at 360°C for 4h, and finally water and graphite were added to form tablets to obtain catalyst C5.

[0038] Example 6

[0039] SiO2:Al2O3 molar ratio of 2:1 Weigh 40% silica sol 438g, aluminum hydroxide 227.76g, NaOH 160g, dissolve in 4.5L deionized water to make a solution, add to a stirred reactor, react at 60°C for 30min; according to the molar ratio of Cu:Zn:Zr = 1:1.5:1, weigh Cu(NO3)2187.56g, Zn(NO3)2284.1g, Zr( NO3)2·5H2O429.3g was dissolved in 2L of deionized water to prepare a mixed solution; the mixed solution was added into a reactor and the reaction time was controlled to be 40min; the obtained catalyst precursor was placed into a pressure autoclave with stirring and hydrothermally treated at 160°C for 4h; the product was poured out, washed, filtered, and dried, 54g of lanthanum oxide additive was added, granulated, and calcined at 360°C for 4h, and finally water and graphite were added to form tablets to obtain catalyst C6.

[0040] Example 7

[0041] The molar ratio of SiO2:Al2O3 is 3:1. 565.5g of 40% silica sol, 431.1g of aluminum sulfate, and 336g of KOH are weighed and dissolved in 4L of deionized water to prepare a solution, which is added to a stirred reactor and reacted at 60°C for 30min. According to the molar ratio of Cu:Zn:Zr=1:1:1, 187.56g of Cu(NO3)2, 189.4g of Zn(NO3)2, and 29.3g of Zr(NO3)2·5H2O4 are weighed and dissolved in 2L of deionized water to prepare a mixed solution. The mixed solution is added to the reactor and the reaction time is controlled to 40min. The obtained catalyst precursor is placed in a stirred pressure autoclave and hydrothermally treated at 160°C for 4h. The product is poured out, washed, filtered, dried, magnesium oxide additive is added, granulated, and roasted at 360°C for 4h. Finally, water and graphite are added to form tablets to obtain catalyst C7.

[0042] Example 8

[0043] The catalyst was applied to the hydrogenation of isononanal to produce isononanol.

[0044] Take 50 ml of C1-C7 catalyst and load it into a fixed bed reactor. Before the reaction, reduce the catalyst at 180°C, 0.2 MPa, and 5% hydrogen concentration in nitrogen and hydrogen atmosphere for 12 h. Then raise the temperature to 200°C, the reaction pressure to 3 MPa, and feed the isononaldehyde at a rate of 0.6 h. -1 , H2 flow rate 300ml / min, the results are shown in Table 1.

[0045] Table 1 Activity evaluation results

[0046] Serial number Isononanal conversion rate / % Isononanol selectivity / % C1 99.7 99.2 C2 99.3 98.5 C3 99.2 98.2 C4 99.6 99.1 C5 99.7 99.4 C6 99.1 98.8 C7 99.0 98.2 .

[0047] It can be seen from the data in Table 1 that when the catalyst designed by the technical solution of the present invention is applied to the reaction of hydrogenating isononanal to produce isononanol, the conversion rate of isononanal reaches more than 99%, the selectivity of isononanol reaches more than 98%, and the catalyst performance is good.

[0048] Example 9

[0049] Take 50 ml of C1 catalyst and load it into a fixed bed reactor. Before the reaction, reduce the catalyst at 180°C, 0.2 MPa, and 5% hydrogen concentration in nitrogen and hydrogen atmosphere for 12 h. Then raise the temperature to 250°C, the reaction pressure to 3 MPa, and the isononanal feed rate to 0.6 h- 1 , H2 flow rate 300ml / min, the results are shown in Table 2.

[0050] Example 10

[0051] Take 50 ml of Cl catalyst and load it into a fixed bed reactor. Before the reaction, reduce the catalyst at 180°C, 0.2 MPa, and 5% hydrogen concentration nitrogen and hydrogen atmosphere for 12 hours, cool to 120°C, reaction pressure 4 MPa, and isononanal feed rate 0.6 h- 1 , H2 flow rate 300ml / min, the results are shown in Table 2.

[0052] Table 2 Effect of reaction conditions on activity evaluation results

[0053]

[0054] It can be seen from Table 2 that at a reaction temperature of 120°C-250°C and a reaction pressure of 3-4MPa, the catalyst exhibits excellent catalytic effects. The catalyst has excellent stability, is suitable for industrial reaction conditions, and is conducive to industrial promotion.

Claims

1. An application of a catalyst for hydrogenating isononanal to isononanol, characterized in that: The catalyst is used for the hydrogenation of isononanal to isononanol, the reaction temperature is 120-250°C, and the reaction pressure is 3-4MPa; the catalyst comprises an active component, a carrier and an auxiliary agent, and the active component: the carrier: the auxiliary agent is 20%-40%: 50%-80%: 1%-10% by mass percentage; The active component is one of Cu-Zn alloy, Cu-Zr alloy and Cu-Zn-Zr alloy; the molar ratio of the alloy is Cu:Zn=1:(1-2.5), Cu:Zr=1:(0.5-1), Cu:Zn:Zr=1:(0.5-1.5):(0.5-1); The carrier is aluminosilicate, wherein the molar ratio of SiO2:Al2O3 is (4-1):1; The auxiliary agent is at least one of potassium oxide, magnesium oxide and lanthanum oxide; The preparation method of the catalyst comprises the following steps: 1) Adding silica sol, aluminum nitrate or aluminum sulfate or aluminum hydroxide, and alkaline precipitant solution into a stirred reactor, reacting at 60-90° C. for 20-40 min; the alkaline precipitant is one of NaOH, KOH, Na2CO3, and K2CO3; 2) Mix the nitrate solution of the active component and slowly add it to the reactor in step 1), controlling the reaction time to 20-40 min; 3) placing the catalyst precursor obtained in step 2) into a stirred autoclave and subjecting it to hydrothermal treatment at 120-160° C. for 2-8 h; 4) washing the product in step 3), filtering, drying, adding auxiliary agents, granulating, calcining, and finally adding water and graphite to form tablets to obtain a catalyst; the calcination temperature is 350° C.-400° C., and the calcination time is 2-4 hours.

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