CATALYST FOR PRODUCING DIBASIC AMINE BY HYDROGENATION OF DIBASIC NITRILE, A PROCESS FOR PREPARING THE SAME AND USE THEREOF

Abstract

A catalyst for producing dibasic amine by hydrogenation of dibasic nitrile contains the following components or reaction product thereof: a) an active component, wherein the active component comprises Ni and/or an oxide thereof; b) an auxiliary, wherein the auxiliary comprises one or more of Mg, Cu, Co, Zn, Zr, Mo and/or oxides thereof; C) support, wherein the relative content of α-NiO in the catalyst is less than 2.0 a.u. A process for producing dibasic amine by hydrogenation of dibasic nitrile is also provided.

Claims

1. A catalyst, which comprises: a) an active component, wherein the active component comprises an oxide of Ni; b) an auxiliary, preferably, the auxiliary comprises one or more of oxides of Mg, Cu, Co, Zn, Zr, and Mo, more preferably the auxiliary comprises one or more of oxides of Cu, Co, Zr, and Mo; c) a support; wherein, the relative content of α-NiO in the catalyst is less than 2.0 a.u., for example less than 1.5 a.u., further for example less than 0.2 a.u.

2. The catalyst according to claim 1, which is characterized in that based on the parts by weight, the content of the active component is 10-60 parts, for example 15-55 parts; the content of the auxiliary is 0.1-120 parts, for example 0.2-90 parts; The content of said support is 0.1-45 parts, for example 1-35 parts.

3. The catalyst according to claim 1, which is characterized in that said support is at least one of alumina, silica and zeolite, for example alumina; preferably, said support is a support that has been treated at a temperature of not less than 500° C.

4. The catalyst according to claim 1, which is characterized in that said support comprises alumina, wherein based on the weight of alumina, the proportions of α, β, γ, δ, θ-alumina are 0.1-99%, 0.1-99%, 0.1-99%, 0.1-99%, 0.1-99% respectively, preferably 10-95%, 1-70%, 2-90%, 5-90%, 3-80% respectively.

5. The catalyst according to claim 1, which is characterized in that the catalyst is a catalyst for producing dibasic amine by hydrogenation of dibasic nitrile.

6. The catalyst according to claim 1, which is characterized in that the relative content of α-NiO in the catalyst is greater than 0.0001 a.u., for example greater than 0.001 a.u., further for example greater than 0.01 a.u.; or the content of α-NiO in the catalyst is greater than 0.0001 wt %, for example greater than 0.001 wt %, further for example greater than 0.01 wt %.

7. A process for preparing the catalyst according to claim 1, which is characterized in that said process comprises the following steps: 1) performing the first contact of a solution of auxiliary salt, a solution of first precipitant, a support and water to produce a modified support; 2) performing the second contact of a solution of nickel salt, a solution of second precipitant, the modified support obtained from step 1) and water, filtering, and calcining to produce a catalyst, for example, in step 1), the solution of auxiliary salt and the solution of first precipitant are simultaneously added to the water containing the support to perform the first contact, and/or in step 2), the solution of nickel salt and the solution of second precipitant are simultaneously added to the water containing the modified support obtained from step 1) to perform the second contact.

8. The process according to claim 7, which is characterized in that in step 1), the used support is a support that has been treated at a temperature of not less than 500° C., preferably the used support is a support that has been treated at a temperature of higher than 500° C.

9. The process according to claim 7, which is characterized in that the resulting solution in the first contact and the resulting solution in the second contact are controlled to the endpoint pH of 6.0-10.0, for example 6.0-8.0, for example, the temperature of said first contact and/or second contact is 50-90° C., and/or the time of said first contact and/or second contact is 3-6 hours.

10. The process according to claim 7, which is characterized in that said auxiliary salt is selected from one or more of Mg(NO.sub.3).sub.2, Cu(NO.sub.3).sub.2, Co(NO.sub.3).sub.2, Zn(NO.sub.3).sub.2, Zr(NO.sub.3).sub.4, (NH.sub.4).sub.2MoO.sub.4, Mg(NO.sub.3).sub.2.Math.6H.sub.2O, Cu(NO.sub.3).sub.2.Math.3H.sub.2O, Co(NO.sub.3).sub.2.Math.6H.sub.2O, Zn(NO.sub.3).sub.2.Math.6H.sub.2O and Zr(NO.sub.3).sub.4.Math.5H.sub.2O, for example selected from one or more of Cu(NO.sub.3).sub.2, Zr(NO.sub.3).sub.4, (NH.sub.4).sub.2MoO.sub.4 and Co(NO.sub.3).sub.2; and/or said first precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, preferably, the first precipitant is carbon-free, more preferably, the first precipitant is sodium hydroxide and/or ammonia water; and/or the nickel salt is nickel sulphate and/or nickel nitrate, for example nickel nitrate; and/or said second precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, preferably, said second precipitant is carbonaceous, more preferably said second precipitant is sodium carbonate and/or sodium bicarbonate.

11. The process according to claim 7, which is characterized in that in step 1), said solution of auxiliary salt has a concentration of 0.1-1.5 mol/L, for example 0.3-1.2 mol/L; and/or said solution of first precipitant has a concentration of 0.4-2.0 mol/L, for example 0.6-1.6 mol/L; and/or the content of said support in water is 5-100 g/L, for example 20-80 g/L, or 5-20 g/L, e.g. 8-15 g/L.

12. The process according to claim 7, which is characterized in that in step 2), said solution of nickel salt has a concentration of 0.2-1.5 mol/L, for example 0.5-1.2 mol/L; and/or said solution of second precipitant has a concentration of 0.4-2.0 mol/L, for example 0.6-1.5 mol/L, and/or the content of said support in water is 10-100 g/L, for example 20-85 g/L, or 10-30 g/L, e.g. 12-25 g/L.

13. A process for producing dibasic amine by hydrogenation of dibasic nitrile, comprising in the presence of the catalyst according to claim 1, the dibasic nitrile is contacted with hydrogen gas to generate the dibasic amine, for example, the molar ratio of hydrogen gas to dibasic nitrile is 3:1-70:1, for example 5:1-20:1, for example, the reaction temperature is 50-120° C., for example 60-80° C.; and/or said reaction pressure is 4.0-15.0 MPa, for example 4.0-12.0 MPa, further for example 6.0-10.0 MPa; and/or the liquid hourly space velocity of said reaction is 1-12 hr.sup.−1, for example 2-10 hr.sup.−1.

14. Use of the catalyst according to claim 1 in producing dibasic amine by hydrogenation of dibasic nitrile, especially in producing aliphatic C.sub.4-C.sub.24 dibasic amine (such as hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, or octadecanediamine) or aromatic C.sub.6-C.sub.18 dibasic amine (such as ortho-benzenedimethanamine, meta-benzenedimethanamine, or para-benzenedimethanamine) by hydrogenation of aliphatic C.sub.4-C.sub.24 dibasic nitrile (such as adiponitrile, pimelonitrile, suberonitrile, nonanedinitrile, decanedinitrile, undecanedinitrile, dodecanedinitrile, tridecanedinitrile, tetradecanedinitrile, pentadecanedinitrile, hexadecanedinitrile, heptadecanedinitrile, or octadecanedinitrile) or aromatic C.sub.6-C.sub.18 dibasic nitrile (such as phthalonitrile, isophthalonitrile, or terephthalonitrile).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0114] FIG. 1 shows the H.sub.2-TPR diagrams of the catalysts prepared in Examples 1 and 2 and Comparative Example 1.

wherein (1) α-NiO (300-400° C.): attributed to free amorphous NiO species on the surface; (2) β1-NiO (400-500° C.): attributed to the NiO species weakly interacting with the support; (3) β2-NiO (500-600° C.): attributed to the NiO species strongly interacting with the support.

DETAILED DESCRIPTION

[0115] In order to make the present invention easier to understand, the present invention will be described in detail below in conjunction with the embodiments and accompanying drawings. These embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The used reagents or instruments, for which the manufacturers are not indicated herein, are commercially available or obtained by conventional methods.

[0116] The end points of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include the values close to these ranges or values. For numerical ranges, the endpoints of the ranges to each other, the endpoints of the ranges and the individual point values, and the individual point values to each other can be combined with each other to give one or more new numerical ranges, and these new numerical ranges should be construed as specifically disclosed herein.

[0117] In the concept used in the present invention, the conversion ratio and the selectivity for producing m-xylylenediamine by hydrogenation of isophthalonitrile are calculated by the following equations:

[00001] $IPN conversion ratio = \frac{n_{IPN, 1} - n_{IPN, 2}}{n_{IPN, 1}} \times 100 % MXDA selectivity = \frac{n_{MXDA, 2}}{n_{IPN, 1} - n_{IPN, 2}} \times 100 %$

in which, n: the amount of substance, in unit of mol; IPN: isophthalonitrile; MXDA: m-xylylenediamine; 1: raw materials; 2: product.

Test Method:

[0118] 1. The test method for the relative content of different types of NiO: the area integration of the H.sub.2-TPR curve (the ordinate is % TCD, and the abscissa is temperature) is performed, and the relative content of different types of NiO is calculated based on the hydrogen consumption of the sample, and the unit is a.u. (arbitrary unit). The size of the peak area actually represents the relative content of different types of NiO, and is used for the mutual comparison of NiO between different samples.

[0119] In the following examples, the isophthalonitrile used is of the industrial grade and dissolved in liquid ammonia, the mass fraction of isophthalonitrile is 10%, and the mass fraction of liquid ammonia is 90%; the volume fraction of the used hydrogen gas is 99.9%.

[0120] The constitution of the catalyst is measured according to the X-ray fluorescence method (with reference to “Petrochemical Analysis Method (RIPP Test Method)”, edited by Yang Cuiding et al., Science Press, published in 1990).

Example 1

(1) Catalyst Preparation

[0121] Preparation of modified support: the auxiliary salt Co(NO.sub.3).sub.2 was made into a solution I with a concentration of 0.8 mol/L, sodium hydroxide was made into a solution II with a concentration of 1.0 mol/L, and the precursor of the aluminum hydroxide support (pseudo-boehmite) was pretreated at a high temperature of 500° C. and placed in 1 L of water. At 70° C., solution I and solution II were co-currently precipitated, and the endpoint pH was controlled to 7.0. The aging while stirring was performed for 3-6 hours to produce a modified alumina support.

[0122] Preparation of catalyst: nickel nitrate was made into a solution III with a concentration of 0.8 mol/L, sodium carbonate was made into a solution IV with a concentration of 1.2 mol/L, and the obtained modified alumina support (50 g) was placed in 1 L of water. At 70° C., solution III and solution IV were co-currently precipitated, and the endpoint pH was controlled to 7.5. The aging while stirring was performed for 4 hours, and then filtering, washing, drying, and calcining in the air atmosphere at 500° C. for 6 hours were performed to produce a catalyst. In the resulting catalyst, the weight of CoO was 0.75 g, the weight of the active component as nickel oxide was 5.25 g, and the weight of the alumina support was 9.0 g. The H.sub.2-TPR diagram was shown in FIG. 1, and the results were shown in Table 1.

(2) Catalyst Reduction

[0123] 15 g of the obtained catalyst was taken, which contained CoO (0.75 g) in the catalyst components. The catalyst was loaded to 15 mL, and reduced with pure hydrogen gas at 500° C. for 24 hours to produce a reduced catalyst.

(3) Producing m-Xylylenediamine by Hydrogenation of Isophthalonitrile

[0124] A solution of isophthalonitrile in liquid ammonia (3000 mL, the mass fraction of isophthalonitrile was 10%, the mass fraction of liquid ammonia was 90%) and a pure hydrogen gas (the volume fraction of hydrogen gas was 99.9%) were used as raw materials, the used amount of the reduced catalyst was 15 g, and the hydrogenation test was performed under the following conditions: the reaction temperature was 80° C., the reaction pressure was 8.0 MPa, the hydrogen gas/isophthalonitrile molar ratio was 5:1, and the liquid hourly space velocity was 10 hr.sup.−1. The reaction results were shown in Table 1. The IPN conversion rate was 99.9%, the MXDA selectivity was 97.1%. The content of 3-methylbenzylamine was 0.32% (measured by liquid chromatography).

Example 2

[0125] The catalyst of this example was prepared by the preparation method of the catalyst in Example 1, except that a different content of Co was used in the catalyst: the weight of CoO in the catalyst was 2.25 g. The H.sub.2-TPR diagram was shown in FIG. 1, and the results were shown in Table 1.

(1) Catalyst Reduction:

[0126] 15 g of the catalyst was taken, which contained CoO (2.25 g) in the catalyst. The catalyst was loaded to 15 mL, and reduced with pure hydrogen gas at 500° C. for 24 hours to produce a reduced catalyst.