Continuous production method of 1, 3-cyclohexanedimethylamine

Abstract

The invention relates to the technical field of synthesis of amine compounds, and discloses a continuous production method of 1, 3-cyclohexanedimethylamine, a naphthylamine compound and H12MDA are added into raw materials, the naphthylamine compound and the H12MDA are adsorbed on the surface of a catalyst to generate a synergistic effect, in the process of generating MXDA through MXPN hydrogenation, the adsorption of H2 and MXPN by the active surface of the catalyst can be promoted, the reaction rate is increased, and the yield of MXDA is increased. In addition, rapid desorption of the product MXDA is facilitated, so that side reactions are inhibited, and the selectivity of the MXDA is improved. Besides, in the process of generating the 1, 3-BAC through hydrogenation of the MXDA, through adsorption modulation of the active site and the acid-base site of the catalyst, the hydrogenation reaction rate of the MXDA can be increased, side reactions are inhibited, and the hydrogenation reaction of the MXDA can be dynamically carried out towards a path which is more beneficial to generation of cis-1, 3-BAC through the spatial directional induction effect, so that the cis-enriched 1, 3-BAC is obtained.

Description

Technical Field

[0001] This invention relates to the field of amine compound synthesis technology, specifically to a continuous production method for 1,3-cyclohexanedimethylamine. Background Technology

[0002] 1,3-Cyclohexanedimethylamine (1,3-BAC, structure shown below) is an important fine chemical intermediate. Due to its advantages such as low freezing point, high low-temperature curing activity, resistance to yellowing, and low toxicity, it can be widely used in fields such as tile grout and automotive composite materials. Commercially available 1,3-BAC is usually a mixture of cis-1,3-BAC and trans-1,3-BAC. 1,3-BAC with a higher cis-1,3-BAC content generally exhibits better application performance. For example, nylon synthesized from cis-rich 1,3-BAC has higher crystallinity and better mechanical properties, heat resistance, and chemical stability.

[0003]

[0004] Currently, 1,3-BAC is produced industrially by converting m-xylene into isophthalonitrile (MXPN) through ammonia oxidation, then converting MXPN into m-phenylenediamine (MXDA) through hydrogenation, and finally preparing 1,3-BAC through further hydrogenation of MXDA.

[0005] The following are existing reports on the hydrogenation technology of MXDA to prepare 1,3-BAC: Chinese patent document CN109772312A uses 4% Ru / hydrotalcite as a catalyst and modifies the catalyst with lithium hydroxide. Tetrahydrofuran is used as a solvent, the reaction temperature is 130℃, the pressure is 5MPa, and MXDA hydrogenation is carried out in a batch process, achieving a conversion rate of 100% and a 1,3-BAC selectivity of 96.1%.

[0006] Chinese patent document CN102690203A uses 5%Ru-1%Pd / Al2O3 as a catalyst and liquid ammonia as a solvent. With a substrate mass concentration of 20% and a catalyst dosage of 0.2 times the mass of MXDA, the reactor is charged with hydrogen to 10 MPa and then heated to 130℃. The reaction is carried out at this temperature for 10 h, resulting in a conversion rate of 99.9% for MXDA and a selectivity of 97.3% for 1,3-BAC.

[0007] US Patent Document US5741928A describes the use of a 2% loaded Ru / Al2O3 catalyst for continuous fixed-bed hydrogenation of MXDA. Liquid ammonia, 1,3-BAC, diethylamine, triethylamine, or mixtures thereof with alcohols are used as solvents. The reaction is carried out at a temperature of 120°C and a pressure of 10 MPa, yielding a molar yield of 95% for 1,3-BAC.

[0008] There are also a few reports on the one-step hydrogenation preparation of 1,3-BAC using MXPN: US Patent document US5371293A discloses a method for one-step hydrogenation of aromatic dinitrile to prepare cyclohexanedimethylamine. Using a Ru / Al₂O₃ catalyst with a Ru loading of 1%-10%, liquid ammonia or a mixture of ammonia and dioxane as a solvent, the MXPN is hydrogenated at a reaction temperature of 70℃-150℃ and a pressure of 50 atm-150 atm, yielding 1,3-BAC in a molar yield of 88%.

[0009] US Patent document US4070399A discloses a method for one-step hydrogenation of terephthalonitrile to prepare 1,4-cyclohexanedimethylamine (1,4-BAC). The method uses an alumina-supported Ru-Pd bimetallic catalyst and liquid ammonia or a mixed solvent of ammonia or dioxane, diethylamine, etc. to obtain 1,4-BAC with a mass yield of up to 99 wt%.

[0010] There have also been a few reports on techniques for increasing the cis-isocyanate content in 1,3-BAC products through isomerization: Chinese patent CN105555754A discloses a method for isomerizing 1,3-BAC with a cis-containing content of 74% by using 4-methylbenzaldehyde and sodium amino at a certain temperature, increasing the cis-containing content to 80% and achieving an isomerization yield of 94%.

[0011] In summary, most existing technologies use MXDA as a raw material to prepare 1,3-BAC through intermittent hydrogenation. The main problems are: (1) Using MXDA as a raw material to prepare 1,3-BAC is equivalent to using MXPN as a raw material to prepare 1,3-BAC through two-step hydrogenation. The two-step hydrogenation has significant differences in catalysts, solvents and operating conditions. Furthermore, the reaction liquid obtained by hydrogenating MXPN needs to be desolvated, distilled and other post-processed to obtain high-purity MXDA, which is then supplied to the downstream process for further hydrogenation to obtain 1,3-BAC. Overall, there are problems such as long process route, low product yield, complicated operation, high equipment investment and high energy consumption, resulting in high production cost and low efficiency; (2) In order to improve the selectivity and yield of MXPN hydrogenation, Chinese patent documents CN111036226A and CN110560065A generally introduce a large amount of liquid ammonia into the reaction system as a solvent and deamination inhibitor. Although US patent document US5371293A uses MXPN for one-step hydrogenation synthesis of 1,3-BAC, which simplifies the process, it also introduces a large amount of liquid ammonia into the reaction system in order to suppress side reactions. The use of large amounts of liquid ammonia poses a risk of leakage and can easily pollute the production environment. Furthermore, the recovery of liquid ammonia is difficult and significantly increases production costs. (3) US patent documents US5371293A and US4070399A use MXPN and p-xylene (PXPN) one-step hydrogenation processes to synthesize 1,3-BAC and 1,4-BAC, respectively. However, both use batch processes, resulting in low production efficiency. Moreover, both have problems such as large catalyst usage and easy deactivation when reused. (4) Existing technologies, such as Chinese patent document CN105555754, disclose that isomerization treatment can increase the cis-iso group content in 1,3-BAC products. However, this process uses a large amount of 4-methylbenzaldehyde and sodium amino acid, which is not only costly but also poses a high safety risk. In addition, this process will also cause a certain loss of 1,3-BAC. This is an ideal technology for the preparation of non-cis-rich 1,3-BAC. Summary of the Invention

[0012] In view of this, the technical problem to be solved by the present invention is that the existing production methods of 1,3-cyclohexanedimethylamine have the defects of being environmentally unfriendly and having low selectivity for cis-1,3-BAC. The present invention provides a production method of 1,3-cyclohexanedimethylamine with an environmentally friendly and safe preparation process and high selectivity for cis-1,3-BAC.

[0013] In a first aspect, the present invention provides a continuous production method for 1,3-cyclohexanedimethylamine, comprising the following steps: The raw material was sequentially contacted with catalyst A and catalyst B to carry out the first hydrogenation reaction and the second hydrogenation reaction, to obtain 1,3-cyclohexanedimethylamine. The raw materials include naphthylamine compound, 4,4'-diaminodicyclohexylmethane, isophthalonitrile and solvent; Catalyst A includes a supported Ni-Ru catalyst; catalyst B includes a supported Ru-Rh catalyst; The mass percentage of the anti-antibody in the 4,4'-diaminodicyclohexylmethane is 8%-30%.

[0014] As an example, the mass percentage of the anti-antibody in the 4,4'-diaminodicyclohexylmethane is 8%, 10%, 12%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, or 30%.

[0015] It should be noted that the present invention uses two reactors connected in series to carry out a two-step continuous hydrogenation reaction.

[0016] In some optional embodiments, the mass ratio of the isophthalonitrile to the naphthylamine compound is 1:0.001-0.15, optionally 1:0.1-0.15.

[0017] As an example, the mass ratio of the isophthalonitrile to the naphthylamine compound is 1:0.001, 1:0.005, 1:0.01, 1:0.015, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, or 1:0.15.

[0018] In some optional embodiments, the mass ratio of isophthalonitrile to 4,4'-diaminodicyclohexylmethane is 1:0.001-1, optionally 1:0.01-0.1.

[0019] As an example, the mass ratio of the isophthalonitrile to the 4,4'-diaminodicyclohexylmethane is 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1.

[0020] In some optional embodiments, the 4,4'-diaminodicyclohexylmethane contains 12%-20% by mass of the anti-antibody.

[0021] In some optional embodiments, the naphthylamine compound includes at least one selected from 1-naphthylamine, 2-naphthylamine, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, N,N-dimethyl-1-naphthylamine, N,N-diethyl-1-naphthylamine, N-methyl-2-naphthylamine, N-ethyl-2-naphthylamine, N,N-dimethyl-2-naphthylamine, 4-bromo-1-naphthylamine, 8-bromo-1-naphthylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1,3-naphthyldiamine, 1,4-naphthyldiamine, 1,5-naphthyldiamine, 1,7-naphthyldiamine, 1,8-naphthyldiamine, 2,6-naphthyldiamine, 1,1'-bi-2-naphthylamine, and N,N'-dimethyl-1,1'-bi-2-naphthylamine; optionally, it is at least one selected from 1,5-naphthyldiamine, 2,6-naphthyldiamine, and 1,1'-bi-2-naphthylamine.

[0022] In some optional embodiments, the temperature of the first hydrogenation reaction is 40°C-200°C, optionally 60°C-140°C; the pressure is 2MPa-25MPa, optionally 5MPa-15MPa.

[0023] As an example, the temperature of the first hydrogenation reaction is 40°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, or 200°C; and the pressure is 2MPa, 4MPa, 6MPa, 8MPa, 10MPa, 12MPa, 14MPa, 16MPa, 18MPa, 20MPa, 22MPa, or 25MPa.

[0024] In some alternative embodiments, the temperature of the second hydrogenation reaction is 60°C-220°C, optionally 80°C-150°C, and the pressure is 2MPa-25MPa, optionally 5MPa-15MPa.

[0025] As an example, the temperature of the second hydrogenation reaction is 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, or 220°C; and the pressure is 2MPa, 4MPa, 6MPa, 8MPa, 10MPa, 12MPa, 14MPa, 16MPa, 18MPa, 20MPa, 22MPa, or 25MPa.

[0026] In some alternative embodiments, the solvent comprises a mixture of methanol and organic amines.

[0027] In some optional embodiments, the organic amine includes at least one selected from 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, ethanolamine, isopropanolamine, tert-butylamine, diethylenetriamine, hexanediamine, and pentanediamine; optionally, it is at least one selected from 1,3-cyclohexanedimethylamine and tert-butylamine.

[0028] In some optional embodiments, the mass ratio of methanol to organic amine is 1:0.001-200, optionally 1:0.05-50.

[0029] As an example, the mass ratio of methanol to organic amine is 1:0.001, 1:0.01, 1:0.1, 1:1, 1:20, 1:40, 1:60, 1:80, 1:100, 1:120, 1:140, 1:160, 1:180, or 1:200.

[0030] In some optional embodiments, the mass ratio of isophthalonitrile to the solvent is 1:5-10000, optionally 1:10-1000.

[0031] As an example, the mass ratio of the isophthalonitrile to the solvent is 1:5, 1:50, 1:100, 1:500, 1:1000, 1:3000, 1:5000, 1:7000, or 1:10000.

[0032] In some optional embodiments, the feed space velocity, expressed as the ratio of isophthalonitrile feed mass to catalyst A mass per unit time, is 0.01-50 g. 间苯二甲腈 ·g 催化剂A -1 ·h -1 The dosage can be selected from 0.1-10g. 间苯二甲腈 ·g 催化剂A -1 ·h -1 .

[0033] As an example, the feed space velocity, expressed as the ratio of isophthalonitrile feed mass to catalyst A per unit time, is 0.01 g. 间苯二甲腈 ·g 催化剂A -1 ·h -1 0.05g 间苯二甲腈 ·g 催化剂A -1 ·h -1 0.1g 间苯二甲腈 ·g 催化剂A -1 ·h -1 0.5g 间苯二甲腈 ·g 催化剂A -1 ·h -1 1g 间苯二甲腈 ·g 催化剂A -1 ·h -1 5g 间苯二甲腈 ·g 催化剂A-1 ·h -1 10g 间苯二甲腈 ·g 催化剂A -1 ·h -1 20g 间苯二甲腈 ·g 催化剂A -1 ·h -1 30g 间苯二甲腈 ·g 催化剂A -1 ·h -1 40g 间苯二甲腈 ·g 催化剂A -1 ·h -1 Or 50g 间苯二甲腈 ·g 催化剂A -1 ·h -1 .

[0034] In some optional embodiments, the molar ratio of hydrogen intake per unit time to isophthalonitrile feed rate is 10-1000:1, optionally 20-100:1.

[0035] As an example, the molar ratio of hydrogen intake per unit time to isophthalonitrile feed is 10:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, or 1000:1.

[0036] In some optional embodiments, the catalyst A comprises an active component MA, an auxiliary agent NA, and a support LA. The active component MA comprises Ni and Ru. The auxiliary agent NA comprises at least one of Li, Na, K, Ca, Mg, Zn, B, Be, Sr, and Ba, and optionally at least one of Li and Zn. The support LA comprises at least one of alumina, activated carbon, zirconium oxide, titanium oxide, magnesium oxide, silicon oxide, lanthanum oxide, cerium oxide, calcium carbonate, and diatomaceous earth, and optionally at least one of alumina and zirconium oxide.

[0037] In some optional embodiments, the catalyst B comprises an active component MB, an auxiliary agent NB, and a support LB. The active component MB comprises Ru and Rh. The auxiliary agent NB comprises at least one of Ti, Zr, Ga, Fe, Co, Cu, Ni, Ag, and Mo, and optionally at least one of Fe and Mo. The support LB comprises at least one of alumina, activated carbon, zirconium oxide, titanium oxide, magnesium oxide, silicon oxide, lanthanum oxide, cerium oxide, calcium carbonate, and diatomaceous earth, and optionally alumina. According to the crystal form classification, the alumina is selected from at least one of γ-Al₂O₃, η-Al₂O₃, δ-Al₂O₃, θ-Al₂O₃, κ-Al₂O₃, and α-Al₂O₃, and more preferably θ-Al₂O₃.

[0038] In some optional embodiments, the mass ratio of catalyst A to catalyst B is 1:0.05-50, and optionally 1:0.5-10.

[0039] As an example, the mass ratio of catalyst A to catalyst B is 1:0.05, 1:0.1, 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 50.

[0040] In some alternative embodiments, in catalyst A, the Ni content is 0.1wt%-80wt%, optionally 1wt%-40wt%; the Ru content is 0.001wt%-20wt%, optionally 0.1wt%-10wt%; and the NA content of the auxiliary agent is 0.001wt%-10wt%, optionally 0.01wt%-1wt%.

[0041] As an example, in catalyst A, the Ni content is 0.1wt%, 1wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, or 80wt%; the Ru content is 0.001wt%, 0.01wt%, 0.1wt%, 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 11wt%, 13wt%, 15wt%, 17wt%, or 20wt%; and the NA content is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, or 10wt%.

[0042] In some optional embodiments, the content ratio of Ni to Ru in catalyst A is 0.1-1000:1, optionally 10-100:1.

[0043] As an example, in the catalyst A, the content ratio of Ni to Ru is 0.1:1, 1:1, 10:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, or 1000:1.

[0044] In some optional embodiments, the catalyst B contains Ru at a content of 0.01wt%-20wt%, optionally 0.1wt%-10wt%; Rh at a content of 0.001wt%-10wt%, optionally 0.01wt%-1wt%; and NB at a content of 0.001wt%-20wt%, optionally 0.01wt%-1wt%.

[0045] As an example, in catalyst B, the Ru content is 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 11wt%, 13wt%, 15wt%, 17wt%, or 20wt%; the Rh content is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 7wt%, or 10wt%; and the auxiliary agent NB content is 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 4wt%, 8wt%, 12wt%, 16wt%, or 20wt%.

[0046] In some alternative embodiments, the content ratio of Ru to Rh in catalyst B is 0.05-100:1, optionally 0.5-50:1.

[0047] As an example, in the catalyst B, the content ratio of Ru to Rh is 0.05:1, 0.1:1, 1:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, or 100:1.

[0048] Compared with the prior art, the technical solution of the present invention has the following advantages: The continuous production method of 1,3-cyclohexanedimethylamine provided by this invention includes the following steps: contacting the raw material sequentially with catalyst A and catalyst B to perform a first hydrogenation reaction and a second hydrogenation reaction to obtain 1,3-BAC; wherein the raw material includes a naphthylamine compound and 4,4'-diaminodicyclohexylmethane (H... 12MDA), MXPN, and a solvent; catalyst A comprises a supported Ni-Ru catalyst; catalyst B comprises a supported Ru-Rh catalyst. This invention adds a naphthylamine compound and a low-reactant H to the raw materials. 12 MDA and MXPN adsorb onto the catalyst surface and exert a synergistic effect. During the hydrogenation of MXPN to MXDA, they not only promote the adsorption of H2 and MXPN on the active surface of the catalyst, increasing the reaction rate, but also facilitate the rapid desorption of MXDA, thereby suppressing side reactions and improving MXDA selectivity. Furthermore, during the hydrogenation of MXDA to 1,3-BAC, the adsorption modulation of active and acid-base sites on the catalyst by both MDA and MXPN not only increases the MXDA hydrogenation reaction rate and suppresses side reactions, but also, through spatial orientation, directs the MXDA hydrogenation reaction kinetically towards a pathway more favorable for the formation of cis-1,3-BAC, ultimately yielding a cis-rich 1,3-BAC product.

[0049] This invention employs a two-step continuous hydrogenation process to prepare 1,3-BAC. This avoids the problems of high equipment investment and energy consumption associated with the two-step hydrogenation process of MXPN to prepare 1,3-BAC, which requires solvent removal and distillation of the crude MXDA product. It also avoids the problems of large catalyst usage and catalyst deactivation associated with the one-step hydrogenation process of MXPN to prepare 1,3-BAC. This effectively reduces production costs and improves production efficiency. Furthermore, it avoids introducing large amounts of liquid ammonia or 4-methylbenzaldehyde and sodium amino groups into the reaction system, resulting in low safety risks and a more environmentally friendly approach.

[0050] Catalyst A includes a supported Ni-Ru catalyst, which, compared to Ni-based catalysts, not only exhibits higher hydrogenation activity of MXPN but also lower levels of side reactions such as intramolecular deamination and intermolecular deamination condensation of MXDA. Catalyst B includes a supported Ru-Rh catalyst, which, compared to Ru-based catalysts, exhibits higher hydrogenation activity of MXDA. Furthermore, the addition of Rh not only improves the selectivity of the cis-form in the product but also provides stability to the catalyst.

[0051] Meanwhile, the present invention controls the content of the anti-antibody of 4,4'-diaminodicyclohexylmethane to be 8%-30%, thereby improving the selectivity of the cis-antibody in the product. If the content of the anti-antibody is too high, it will inhibit the activity of the catalyst. Detailed Implementation

[0052] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0053] Where specific experimental steps or conditions are not specified in the examples, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0054] Gas chromatograph: Agilent 7890B, FID detector, DB-5 capillary column (30m×250μm×0.25μm), injection port temperature 280℃, detector temperature 300℃; temperature program: initial temperature 50℃, hold for 2 min, increase to 80℃ at 5℃ / min, then increase to 300℃ at 15℃ / min, hold for 15 min.

[0055] Quantitative analysis was performed using the external standard method to calculate the raw material conversion rate and product yield.

[0056] The percentage content of cis-1,3-BAC in cis-1,3-BAC was calculated using the peak area normalization method: cis-1,3-BAC content = cis-1,3-BAC peak area / (cis-1,3-BAC peak area + trans-1,3-BAC peak area) × 100%.

[0057] In this invention, isophthalonitrile (MXPN) was purchased from Jiangxi Yangli New Materials Co., Ltd.; catalyst A and catalyst B were purchased from Kangna New Materials (Hangzhou) Co., Ltd.; in this invention, catalyst A comprises 20% Ni-0.5% Ru-0.05% Li / Al2O3 and 40% Ni-4% Ru-1% Zn / ZrO2; in the 20% Ni-0.5% Ru-0.05% Li / Al2O3, the mass content of Ni is 20%, the mass content of Ru is 0.5 wt%, the mass content of Li is 0.05%, and the remainder is Al2O3; in the 40% Ni-4% Ru In the -1%Zn / ZrO2 mixture, Ni has a mass content of 40%, Ru has a mass content of 4%, Zn has a mass content of 1%, and the remainder is ZrO2. Catalyst B comprises 2%Ru-0.5%Rh-0.05%Fe / θ-Al2O3 and 0.5%Ru-0.01%Rh-0.01%Mo / θ-Al2O3. In the 2%Ru-0.5%Rh-0.05%Fe / θ-Al2O3 mixture, Ru has a mass content of 2%, Rh has a mass content of 0.5%, Fe has a mass content of 0.05%, and the remainder is Al2O3, with a specific surface area of ​​108.5 m². 2 / g, with a bulk density of 1.12g / mL and a particle size distribution of 30-70μm; in 0.5%Ru-0.01%Rh-0.01%Mo / θ-Al2O3, the mass content of Ru is 0.5%, the mass content of Rh is 0.01%, the mass content of Mo is 0.01%, and the remainder is Al2O3.

[0058] In this invention, 4,4'-diaminodicyclohexylmethane (H 12 The MDA was purchased from the Functional Chemicals Division of Wanhua Chemical Group, model number WANAMINE® H 12 MDA.

[0059] The present invention will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by the present invention.

[0060] Example 1 This embodiment provides a continuous production method for 1,3-BAC, including the following steps: Two 1L reactors with built-in filters, namely the first reactor and the second reactor, were connected in series. The outlet of the first reactor was connected to the inlet of the second reactor. 400g of methanol and 4g of 20%Ni-0.5%Ru-0.05%Li / Al2O3 catalyst were added to the first reactor, and 400g of methanol and 2g of 2%Ru-0.5%Rh-0.05%Fe / θ-Al2O3 catalyst were added to the second reactor. Both reactors were purged three times each with 1MPa nitrogen and hydrogen gas. The temperature of the first reactor was controlled at 80℃, the pressure at 6MPa, and the stirring speed at 800rpm; the temperature of the second reactor was controlled at 100℃, the pressure at 6MPa, and the stirring speed at 800rpm. The hydrogen inlet flow rate for both the first and second reactors was controlled at 35L / h. A high-pressure pump was used to deliver methanol with a mass content of 88.02%, 1,3-cyclohexanedimethylamine with a mass content of 9.78%, MXPN with a mass content of 1.96%, 1,5-naphthyldiamine with a mass content of 0.2%, and H... 12 A feed mixture containing 0.04% MDA (16% by mass of the anti-antibody) was added to the first reactor at a rate of 204.5 g / h. The discharge rate of the first reactor and the feed rate of the second reactor were both controlled at 204.5 g / h. After the system had been running for 48 hours, samples were taken from the outlet of the second reactor for analysis. Gas chromatography was used for external standard quantitative analysis, which showed that the conversion rate of MXPN was 100.0% and the selectivity of 1,3-BAC was 99.99%. Based on the peak area normalization method, the content of cis-1,3-BAC in the product was 84.2%.

[0061] Example 2 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Embodiment 1, except that H... 12The mass percentage of the MDA anti-antibody was 12%, and the temperature of the first reactor was controlled at 140℃. Samples were taken from the outlet of the second reactor for analysis. Gas chromatography was used for external standard quantitative analysis. The conversion rate of MXPN was 100.0%, and the selectivity for 1,3-BAC was 99.98%. Based on peak area normalization analysis, the content of cis-1,3-BAC in the product was 83.5%.

[0062] Example 3 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Example 1, except that the catalyst in the first reactor is replaced with 1g of 40%Ni-4%Ru-1%Zn / ZrO2, H 12 The mass percentage of the MDA anti-antibody was 28%, and the temperature of the second reactor was controlled at 150℃. Samples were taken from the outlet of the second reactor for analysis. Gas chromatography was used for external standard quantitative analysis. The conversion rate of isophthalonitrile was 100.0%, and the selectivity for 1,3-cyclohexanedimethylamine was 99.89%. Based on peak area normalization analysis, the selectivity for cis-1,3-cyclohexanedimethylamine was 83.2%.

[0063] Example 4 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Embodiment 1, except that 1,5-naphthyldiamine is replaced with the same amount of 1,1'-bi-2-naphthylamine. The temperature of the first reactor is controlled at 60°C, the temperature of the second reactor is controlled at 80°C, the pressure of both reactors is controlled at 15 MPa, and the hydrogen flow rate is 500 L / h. Samples are taken at the outlet of the second reactor for analysis. Gas chromatography is used for external standard quantitative analysis. The MXPN conversion rate is 100.0%, and the selectivity for 1,3-BAC is 99.65%. Based on peak area normalization analysis, the content of cis-1,3-BAC in the product is 81.4%.

[0064] Example 5 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Example 1, except that the 1,3-cyclohexanedimethylamine in the feed mixture is replaced with the same amount of tert-butylamine, and the catalyst in the second reactor is replaced with 20g of 0.5%Ru-0.01%Rh-0.01%Mo / θ-Al2O3. The feed rate of the first reactor is 2000g / h, and the hydrogen flow rate is 1000L / h. According to the peak area normalization method, the MXPN conversion rate is 100.0%, the selectivity of 1,3-BAC is 99.99%, and the cis-1,3-BAC content in the product is 84.5%.

[0065] Example 6 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Example 1, except that 1,5-naphthyldiamine in the feed mixture is replaced with the same amount of 2,6-naphthyldiamine. Samples were taken at the outlet of the second reactor for analysis. Gas chromatography was used for external standard quantitative analysis. The MXPN conversion rate was 100.0%, and the selectivity for 1,3-BAC was 99.96%. Based on peak area normalization analysis, the content of cis-1,3-BAC in the product was 83.9%.

[0066] Example 7 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Embodiment 1, except that 1,5-naphthyldiamine in the feed mixture is replaced with N-methyl-1-naphthylamine. The mass content of methanol in the feed mixture is 45.33%, the mass content of 1,3-cyclohexanedimethylamine is 45.33%, the mass content of MXPN is 9.07%, the mass content of N-methyl-1-naphthylamine is 0.09%, and H... 12 The mass content of MDA (16% of the anti-antibody) was 0.18%, and the hydrogen flow rate was 50 L / h. Samples were taken from the outlet of the second reactor for analysis. Gas chromatography with external standard quantification showed an MXPN conversion rate of 100.0% and a selectivity of 99.92% for 1,3-BAC. Based on peak area normalization, the cis-1,3-BAC content in the product was 82.9%.

[0067] Example 8 This embodiment provides a continuous production method for 1,3-BAC, which is basically the same as the steps in Embodiment 1, except that the mass content of methanol in the feed mixture is 96.93%, the mass content of 1,3-cyclohexanedimethylamine is 1.08%, the mass content of MXPN is 1.96%, the mass content of 1,5-naphthyldiamine is 0.02%, and H... 12 The mass content of MDA (16% of the anti-antibody) was 0.01%. Samples were taken from the outlet of the second reactor for analysis. External standard quantification was performed using gas chromatography. The conversion rate of MXPN was 100.0%, and the selectivity for 1,3-BAC was 99.96%. Based on peak area normalization analysis, the content of cis-1,3-BAC in the product was 82.9%.

[0068] Comparative Example 1 This comparative example provides a continuous production method for 1,3-cyclohexanedimethylamine, which is basically the same as the steps in Example 1, except that the addition of H is omitted. 12The MDA feed mixture contained 88.06% methanol, 9.78% 1,3-cyclohexanedimethylamine, 1.96% MXPN, and 0.2% 1,5-naphthyldiamine. Samples were taken from the outlet of the second reactor for analysis. Gas chromatography with external standard quantification showed a phthalonitrile conversion rate of 99.98% and a selectivity of 97.54% for 1,3-cyclohexanedimethylamine. Based on peak area normalization, the product contained 70.2% cis-1,3-BAC.

[0069] Comparative Example 2 This comparative example provides a continuous production method for 1,3-cyclohexanedimethylamine, which is basically the same as the steps in Example 1, except that the addition of 1,5-naphthyldiamine is omitted, and the mass content of methanol in the feed mixture is 88.20%, the mass content of 1,3-cyclohexanedimethylamine is 9.80%, the mass content of MXPN is 1.96%, and H... 12 The mass content of MDA (16% of the anti-antibody) was 0.04%. Samples were taken from the outlet of the second reactor for analysis. External standard quantification was performed using gas chromatography. The conversion rate of isophthalonitrile was 99.87%, and the selectivity for 1,3-cyclohexanedimethylamine was 95.98%. Based on peak area normalization analysis, the content of cis-1,3-BAC in the product was 71.3%.

[0070] Comparative Example 3 This comparative example provides a continuous production method for 1,3-cyclohexanedimethylamine, which is basically the same as the steps in Example 1, except that H... 12 The trans-isocyanate content in MDA was 50%. Samples were taken from the outlet of the second reactor for analysis. External standard quantification was performed using gas chromatography. The conversion rate of isophthalonitrile was 99.98%, and the selectivity for 1,3-cyclohexanedimethylamine was 98.28%. Based on peak area normalization analysis, the cis-1,3-BAC content in the product was 74.6%.

[0071] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A continuous production method for 1,3-cyclohexanedimethylamine, characterized in that, Includes the following steps: The raw material was sequentially contacted with catalyst A and catalyst B to carry out the first hydrogenation reaction and the second hydrogenation reaction, to obtain 1,3-cyclohexanedimethylamine. The raw materials include naphthylamine compound, 4,4'-diaminodicyclohexylmethane, isophthalonitrile and solvent; Catalyst A includes a supported Ni-Ru catalyst; catalyst B includes a supported Ru-Rh catalyst; The mass percentage of the anti-antibody in the 4,4'-diaminodicyclohexylmethane is 8%-30%.

2. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 1, characterized in that, The mass ratio of isophthalonitrile to the naphthylamine compound is 1:0.001-0.15, optionally 1:0.1-0.

15.

3. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 1, characterized in that, The mass ratio of isophthalonitrile to 4,4'-diaminodicyclohexylmethane is 1:0.001-1, optionally 1:0.01-0.

1.

4. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 3, characterized in that, The mass percentage of the anti-antibody in the 4,4'-diaminodicyclohexylmethane is 12%-20%.

5. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 2, characterized in that, The naphthylamine compounds include at least one selected from 1-naphthylamine, 2-naphthylamine, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, N,N-dimethyl-1-naphthylamine, N,N-diethyl-1-naphthylamine, N-methyl-2-naphthylamine, N-ethyl-2-naphthylamine, N,N-dimethyl-2-naphthylamine, 4-bromo-1-naphthylamine, 8-bromo-1-naphthylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1,3-naphthyldiamine, 1,4-naphthyldiamine, 1,5-naphthyldiamine, 1,7-naphthyldiamine, 1,8-naphthyldiamine, 2,6-naphthyldiamine, 1,1'-bi-2-naphthylamine, and N,N'-dimethyl-1,1'-bi-2-naphthylamine.

6. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 1, characterized in that, The temperature of the first hydrogenation reaction is 40℃-200℃, optionally 60℃-140℃; the pressure is 2MPa-25MPa, optionally 5MPa-15MPa. And / or, the temperature of the second hydrogenation reaction is 60℃-220℃, optionally 80℃-150℃; the pressure is 2MPa-25MPa, optionally 5MPa-15MPa.

7. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 1, characterized in that, The solvent comprises a mixture of methanol and an organic amine; the organic amine comprises at least one selected from 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, ethanolamine, isopropanolamine, tert-butylamine, diethylenetriamine, hexanediamine, and pentanediamine. Optionally, the mass ratio of methanol to organic amine is 1:0.001-200, or optionally 1:0.05-50; And / or, in step (1), the mass ratio of the isophthalonitrile to the solvent is 1:5-10000, optionally 1:10-1000.

8. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 1, characterized in that, The feed space velocity, expressed as the ratio of isophthalonitrile feed mass to catalyst A per unit time, is 0.01-50 g. 间苯二甲腈 ·g 催化剂A -1 ·h -1 The dosage can be selected from 0.1-10g. 间苯二甲腈 ·g 催化剂A -1 ·h -1 ; And / or, the molar ratio of hydrogen intake per unit time to isophthalonitrile feed rate is 10-1000:1, optionally 20-100:

1.

9. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 1, characterized in that, The catalyst A comprises an active component MA, an auxiliary agent NA, and a support LA. The active component MA comprises Ni and Ru. The auxiliary agent NA comprises at least one of Li, Na, K, Ca, Mg, Zn, B, Be, Sr, and Ba. The support LA comprises at least one of alumina, activated carbon, zirconium oxide, titanium oxide, magnesium oxide, silicon oxide, lanthanum oxide, cerium oxide, calcium carbonate, and diatomaceous earth. And / or, the catalyst B comprises an active component MB, an auxiliary agent NB, and a support LB, wherein the active component MB comprises Ru and Rh, the auxiliary agent NB comprises at least one of Ti, Zr, Ga, Fe, Co, Cu, Ni, Ag, and Mo; and the support LB comprises at least one of alumina, activated carbon, zirconium oxide, titanium oxide, magnesium oxide, silicon oxide, lanthanum oxide, cerium oxide, calcium carbonate, and diatomaceous earth. And / or, the mass ratio of catalyst A to catalyst B is 1:0.05-50, optionally 1:0.5-10.

10. The continuous production method of 1,3-cyclohexanedimethylamine according to claim 9, characterized in that, In catalyst A, the Ni content is 0.1wt%-80wt%, optionally 1wt%-40wt%; the Ru content is 0.001wt%-20wt%, optionally 0.1wt%-10wt%; and the NA content of the auxiliary agent is 0.001wt%-10wt%, optionally 0.01wt%-1wt%. And / or, in the catalyst A, the content ratio of Ni to Ru is 0.1-1000:1, optionally 10-100:1; And / or, in the catalyst B, the Ru content is 0.01wt%-20wt%, optionally 0.1wt%-10wt%; the Rh content is 0.001wt%-10wt%, optionally 0.01wt%-1wt%; the auxiliary agent NB content is 0.001wt%-20wt%, optionally 0.01wt%-1wt%; And / or, in the catalyst B, the content ratio of Ru to Rh is 0.05-100:1, optionally 0.5-50:1.

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