A kind of preparation method of 2-aminomethylcyclopentylamine

Abstract

The invention discloses a method for preparing 2-aminomethylcyclopentylamine, wherein a continuous fixed bed process is adopted, 1-amino-2-cyanocyclopentene is used as a raw material, and 2-aminomethylcyclopentylamine is obtained by reacting under a hydrogenation catalyst with YSiO3 as a carrier and Ag2O, V5O2 and Gd2O3 as active components. The combination of the hydrogenation catalyst prepared by the invention and a special activation method maximizes the catalytic performance of the hydrogenation catalyst, the raw material conversion rate is as high as 100%, the product selectivity is as high as more than 99%, the catalyst is continuously operated for more than 2000 hours, and has the advantages of high activity, high selectivity and good stability, and has a good industrialization prospect.

Description

Technical Field

[0001] The invention relates to a method for preparing 2-aminomethylcyclopentylamine, and in particular to a method for preparing 2-aminomethylcyclopentylamine by taking 1-amino-2-cyanocyclopentene as a raw material. Background Art

[0002] 2-Aminomethylcyclopentylamine is a valuable amine used in the formulation of epoxy-curing agents for polyurethane crosslinkers, polyamide modifiers, metal chelators and many other applications.

[0003] At present, 2-aminomethylcyclopentylamine is mainly prepared by catalytic hydrogenation of 1-amino-2-cyanocyclopentene. Patent US2292949 discloses a method for preparing 2-aminomethylcyclopentylamine, which uses alumina-supported nickel or finely dispersed, unsupported cobalt catalysts to hydrogenate 1-amino-2-cyanocyclopentene at 2000-3000 psi and 120°C to prepare the diamine. The yield when nickel is used is 36% and when cobalt is used is 59%. For the reaction in the presence of a Group VIII metal catalyst, a hydrogen pressure of 1500 psi is used. The patent has the problem of high reaction pressure and low product yield.

[0004] Patent GB1397576 discloses a method for catalytic hydrogenation of 1-amino-2-cyanocyclopentene in the presence of a powdered Raney nickel catalyst, the catalyst comprising 22-43% nickel, 0.2-1.8% chromium, 1.5-5% iron, and the remainder being aluminum and minor impurities. The reaction is carried out in aqueous sodium hydroxide and ethanol at 93°C and a hydrogen pressure of 1160-1305 psi, and the product yield is only 54%.

[0005] Patent US20040249214A1 discloses a method for preparing 2-aminomethylcyclopentylamine under low pressure, which uses a mixed catalyst system of nickel and carbon-supported palladium or a single palladium-doped Raney nickel catalyst, and reacts for 1-12 hours in a dioxane / water solution at a reaction temperature of 50-150°C and a reaction pressure of 500-1500psi to obtain a crude product, and then obtains a qualified product after separation and purification. This method has the problems of large catalyst dosage, long reaction time, low production efficiency, large excess of liquid ammonia, and environmental pollution caused by dioxane solvent. Summary of the invention

[0006] The purpose of the present invention is to solve the many problems existing in the preparation process of 2-aminomethylcyclopentylamine in the prior art, and to provide a method for preparing 2-aminomethylcyclopentylamine. The method adopts a continuous fixed bed process, uses 1-amino-2-cyanocyclopentene as a raw material, and reacts under a hydrogenation catalyst to obtain 2-aminomethylcyclopentylamine. The combination of the hydrogenation catalyst prepared by the method and a special activation method maximizes the catalytic performance of the hydrogenation catalyst, has the advantages of high activity, high selectivity and good stability, and has a good industrialization prospect.

[0007] In order to achieve the above-mentioned invention object, the present invention adopts the following technical solutions:

[0008] A preparation method of 2-aminomethylcyclopentylamine comprises the steps of using 1-amino-2-cyanocyclopentene as a raw material, reacting in the presence of a hydrogenation catalyst with YSiO3 as a carrier and Ag2O, V5O2 and Gd2O3 as active components to obtain 2-aminomethylcyclopentylamine.

[0009] In a specific embodiment, the active components of the hydrogenation catalyst are supported on a carrier; based on the weight of the carrier, the mass content of each active component is:

[0010] Ag2O 2-15wt%, preferably 5-10wt%;

[0011] V5O2 0.1-2wt%, preferably 0.5-1.5wt%;

[0012] Gd2O3 0.05-1wt%, preferably 0.1-0.5wt%.

[0013] In a specific embodiment, the molar ratio of Si to Y element in the carrier YSiO3 is 1:0.01-1:

[0014] 0.05, preferably 1:0.02-1:0.04.

[0015] In a specific embodiment, the specific surface area of ​​the carrier is 100 m 2 / g-400m 2 / g, preferably 200m 2 / g-300m 2 / g; pore volume is 0.3ml / g-0.8ml / g, preferably 0.5ml / g-0.6ml / g; average pore diameter is 50-200nm, preferably 100-150nm.

[0016] In a specific embodiment, the method for preparing the hydrogenation catalyst comprises the following steps:

[0017] a) preparing a YSiO3 carrier: uniformly mixing a yttrium-containing compound with silicon dioxide, grinding, sieving, drying, calcining, and molding to obtain a carrier;

[0018] b) preparing the catalyst: the carrier obtained in step a) is immersed in an aqueous solution containing soluble silver salt, vanadium salt and gadolinium salt, dried after adsorption equilibrium is reached, and calcined to obtain a catalyst precursor.

[0019] In a specific embodiment, in step a), the drying temperature is 100-200°C, preferably 120-150°C; the drying time is 4-12h, preferably 6-10h; the roasting temperature is 600-1000°C, preferably 750-850°C, and the roasting time is 4-10h, preferably 6-8h.

[0020] In a specific embodiment, in the step b), the impregnation is equal volume impregnation.

[0021] In a specific embodiment, in step b), the drying temperature is 100-200°C, preferably 120-150°C; the drying time is 4-12h, preferably 6-10h; the roasting temperature is 300-600°C, preferably 400-500°C, and the roasting time is 2-8h, preferably 4-6h.

[0022] In a specific embodiment, the hydrogenation catalyst further comprises a step of activating with hydrogen containing ppm-level CO; preferably, 100 mL of hydrogenation catalyst is added to the fixed bed reactor, the activation temperature is 50-150°C, preferably 70-130°C, more preferably 90-110°C; the activation time is 5-15h, preferably 7-12h, more preferably 8-10h.

[0023] In a preferred embodiment, the CO content in the activation step is 50-200 ppm, preferably 80-180 ppm, more preferably 120-150 ppm; the activation pressure is 1-10 MPa, preferably 3-8 MPa, more preferably 5-7 MPa; the volume space velocity of the gas is 0.1-1 L / h / L Cat, preferably 0.3-0.8 L / h / L Cat, more preferably 0.4-0.6 L / h / L Cat.

[0024] In a specific embodiment, the reaction temperature is 150-220°C, preferably 170-200°C, more preferably 180-190°C; the reaction pressure is 0.5-5MPa, preferably 1-4MPa, more preferably 2-3MPa.

[0025] In a preferred embodiment, the space velocity of 1-amino-2-cyanocyclopentene is 0.5-2 L / h / L Cat, preferably 0.8-1.8 L / h / L Cat, more preferably 1.2-1.6 L / h / L Cat; the molar ratio of hydrogen to 1-amino-2-cyanocyclopentene is 3:1-10:1, preferably 4:1-8:1, more preferably 5:1-6:1.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The combination of the hydrogenation catalyst prepared by the present invention and the special activation method maximizes the catalytic performance of the hydrogenation catalyst, has the advantages of high activity, high selectivity and good stability, and has a good industrialization prospect. The raw material conversion rate is 100%, the selectivity is more than 99%, and the catalyst can run continuously and stably for more than 2000 hours.

[0028] The invention introduces Y2O3 into the YSiO3 carrier prepared by solid-state reaction, which, on the one hand, enhances the basicity of the carrier, reduces the acidity of the carrier, and improves the selectivity of the catalyst; on the other hand, enhances the adsorption capacity of the carrier for hydrogen, makes the nitrile hydrogenation reaction easier, and improves the activity of the catalyst; finally, it can inhibit the formation of metal nitrides that cause catalyst deactivation, and further improves the stability of the hydrogenation catalyst.

[0029] The synergistic effect of the active components of Ag2O, V5O2 and Gd2O3 in the hydrogenation catalyst of the present invention greatly improves the activity and selectivity of the catalyst. The introduction of Gd2O3 increases the dispersion and active surface area of ​​Ag2O and V5O2 in the catalyst, thereby improving the activity and selectivity of the catalyst; the introduction of V5O2 inhibits the occurrence of deamination condensation side reactions and enhances the anti-sintering performance of the catalyst.

[0030] The present invention unexpectedly found that after the hydrogenation catalyst of the present invention is activated by hydrogen containing ppm-level CO, the activity, selectivity and stability of the catalyst are further improved. Studies have found that the catalytic performance of the catalyst is optimal when the CO content is in the range of 50-200 ppm, and when the CO content is lower than 50 ppm, the selectivity of the catalyst decreases; when the CO content is higher than 200 ppm, the activity of the catalyst decreases.

[0031] The present invention adopts a continuous fixed bed process, does not need to add any organic solvent, greatly simplifies the post-processing process, has the advantages of simple reaction process, green environmental protection, high production efficiency and suitability for large-scale production. DETAILED DESCRIPTION

[0032] In order to better understand the technical solution of the present invention, the following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the claims of the present invention.

[0033] A method for preparing 2-aminomethylcyclopentylamine comprises taking 1-amino-2-cyanocyclopentene as a raw material and reacting under the action of a hydrogenation catalyst to obtain 2-aminomethylcyclopentylamine, wherein the hydrogenation catalyst comprises a YSiO3 carrier and Ag2O, V5O2 and Gd2O3 active components loaded on the carrier.

[0034] Wherein, the hydrogenation catalyst is prepared by the following method:

[0035] a) preparing a YSiO3 carrier: uniformly mixing a yttrium-containing compound with silicon dioxide, grinding, sieving, drying, calcining, and molding to obtain a carrier;

[0036] b) preparing the catalyst: the carrier obtained in step a) is immersed in an aqueous solution containing soluble silver salt, vanadium salt and gadolinium salt, and after adsorption equilibrium is reached, the carrier is dried and calcined to obtain the catalyst.

[0037] In step a), the yttrium-containing compound is selected from one or more of yttrium nitrate, yttrium sulfate, yttrium hydroxide, yttrium oxalate or yttrium carbonate, preferably yttrium hydroxide and / or yttrium oxalate.

[0038] In the YSiO3 carrier, the molar ratio of Si to Y element is 1:0.01 to 1:0.05, for example, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, etc., preferably 1:0.02 to 1:0.04.

[0039] In the screening process of step a), the mesh size of the solid powder is controlled within the range of 100-200 mesh, such as 110 mesh, 130 mesh, 140 mesh, 150 mesh, 180 mesh, etc., preferably within the range of 120-160 mesh. The screened target powder is dried at a temperature of 100-200°C, such as but not limited to 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, preferably 120-150°C; the drying time is 4-12h, such as but not limited to 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, preferably 6-10h. The dried carrier powder is then calcined at a temperature of 600-1000°C, including but not limited to 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, preferably 750-850°C, and a calcination time of 4-10h, including but not limited to 5h, 6h, 7h, 8h, 9h, 10h, preferably 6-8h.

[0040] The specific surface area of ​​the carrier prepared by the above method is 100m 2 / g-400m 2 / g, preferably 200m 2 / g-300m 2 / g, the pore volume is 0.3ml / g-0.8ml / g, preferably 0.5ml / g-0.6ml / g, and the average pore diameter is 50-200nm, preferably 100-150nm.

[0041] In step b), the soluble silver salt is selected from one or more of silver sulfate, silver nitrate and silver acetate, preferably silver nitrate. The soluble vanadium salt is selected from one or more of vanadium sulfate, vanadium nitrate and vanadium chloride, preferably vanadium nitrate. The soluble gadolinium salt is selected from one or more of gadolinium nitrate, gadolinium oxalate and gadolinium chloride, preferably gadolinium nitrate.

[0042] Wherein, based on the weight of the carrier, the mass content of Ag2O is 2-15wt%, for example, but not limited to 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, preferably 5-10wt%; the mass content of V5O2 is 0.1-2wt%, for example, but not limited to 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1 .0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, preferably 0.5-1.5wt%; the mass content of Gd2O3 is 0.05-1wt%, for example including but not limited to 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, preferably 0.1-0.5wt%.

[0043] The carrier according to the above proportion is impregnated in an aqueous solution containing a soluble silver salt, a vanadium salt and a gadolinium salt. The impregnation is preferably carried out by equal volume impregnation. After adsorption equilibrium is reached, the carrier is dried at a temperature of 100-200°C, for example, including but not limited to 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, preferably 120-150°C; the drying time is 4-12h, for example, including but not limited to 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, preferably 6-10h. After drying, calcination is carried out, the calcination temperature is 300-600°C, for example including but not limited to 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, preferably 400-500°C, and the calcination time is 2-8h, for example including but not limited to 3h, 4h, 5h, 6h, 7h, 8h, preferably 4-6h.

[0044] Under the action of the catalyst prepared by the above preparation method, 1-amino-2-cyanocyclopentene and hydrogen are catalytically hydrogenated to obtain 2-aminomethylcyclopentylamine. Wherein, the reactor is not particularly limited, such as a fixed bed reactor. The reaction temperature is 150-220°C, such as 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, etc., preferably 170-200°C, more preferably 180-190°C; the reaction pressure is 0.5-5MPa, such as 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, etc., preferably 1-4MPa, more preferably 2-3MPa. The space velocity of 1-amino-2-cyanocyclopentene is 0.5-2 L / h / L Cat, for example, 0.6 L / h / L Cat, 0.7 L / h / L Cat, 0.8 L / h / L Cat, 0.9 L / h / L Cat, 1.0 L / h / L Cat, 1.1 L / h / L Cat, 1.2 L / h / L Cat, 1.3 L / h / L Cat, 1.4 L / h / L Cat, 1.5 L / h / L Cat, 1.6 L / h / L Cat, 1.7 L / h / L Cat, 1.8 L / h / L Cat, 1.9 L / h / L Cat, etc., preferably 0.8-1.8 L / h / L Cat, more preferably 1.2-1.6 L / h / L Cat; The molar ratio of hydrogen to 1-amino-2-cyanocyclopentene is 3:1-10:1, for example 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc., preferably 4:1-8:1, more preferably 5:1-6:1.

[0045] In a preferred embodiment, before the catalytic hydrogenation reaction, the step of activating the hydrogenation catalyst is further included. Specifically, the activation step is: adding 100 mL of hydrogenation catalyst to a fixed bed reactor, and activating it with hydrogen containing ppm-level CO. Wherein, the activation temperature is 50-150°C, for example, including but not limited to 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, preferably 70-130°C, more preferably 90-110°C; the CO content is 50-200ppm, for example, including but not limited to 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm pm, 170ppm, 180ppm, 190ppm, preferably 80-180ppm, more preferably 120-150ppm; the activation pressure is 1-10MPa, for example, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, etc., preferably 3-8MPa, more preferably 5-7MPa; the volume space velocity of the gas is 0.1-1L / h / L Cat, for example, 0.2L / h / L Cat, 0.5L / h / L Cat, 0.7L / h / L Cat, 0.9L / h / L Cat, etc., preferably 0.3-0.8L / h / L Cat, more preferably 0.4-0.6L / h / L Cat; the activation time is 5-15h, for example including but not limited to 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, preferably 7-12h, more preferably 8-10h.

[0046] After adopting the above activation steps, the activity, selectivity and stability of the catalyst are further improved.

[0047] The present invention is further explained below by more specific examples, but does not constitute any limitation.

[0048] The main raw material sources of the following examples are as follows:

[0049] 1-Amino-2-cyanocyclopentene: Sinopharm Group, purity ≥99.5wt%.

[0050] Gas chromatograph: Shimadzu GC-2014 (FID) detector, SE-30 capillary column Inlet temperature: 300°C, detector temperature: 270°C; heating program: 100°C, constant temperature for 5 min, then increase to 300°C at a rate of 20°C / min, and hold for 10 min.

[0051] Determination of the content of active components in the catalyst: The content of active metals in the catalyst was measured using a plasma emission spectrometer.

[0052] X-ray diffraction analysis: Shanghai Spectris Instruments Co., Ltd. / PANalytical X Pert3 Powder.

[0053] Example 1

[0054] (1) Preparation of 2wt% Ag2O-2wt% V2O5-0.5wt% Gd2O3 / YSiO3

[0055] 200 g of silicon dioxide and 29.4 g of yttrium oxalate nonahydrate were added to a mortar and mixed evenly. After grinding and sieving, a 100-mesh mixture was obtained. Then, the mixture was transferred to a crucible, dried at 100°C for 12 h, and then calcined in air at 600°C for 10 h (heating rate: 3°C / min; heating rate refers to the temperature rising from room temperature to the final temperature at a certain rate per minute) to obtain YSiO3 white powder (X-ray diffraction analysis shows that the purity of YSiO3 is higher than 98%). After tableting, a 3*3 mm columnar carrier with a specific surface area of ​​300 m 2 / g, the pore volume is 0.3ml / g, and the average pore diameter is 50nm.

[0056] According to the content composition of the catalyst, 100 g of the above-mentioned carrier was immersed in an aqueous solution containing 5.46 g of anhydrous silver nitrate, 15.5 g of ammonium metavanadate and 0.80 g of gadolinium nitrate hexahydrate by an equal volume impregnation method. After adsorption equilibrium was reached, it was dried at 100°C for 12 h and then calcined in air at 300°C for 8 h to obtain a catalyst precursor 2wt% Ag2O-2wt% V2O5 -0.5wt% Gd2O3 / YSiO3.

[0057] (2) Evaluation of catalyst

[0058] The catalyst was evaluated using a continuous fixed bed process, and 100 ml of hydrogenation catalyst was added to the fixed bed reactor. Hydrogen containing 80 ppm CO was used for activation, the activation temperature was 70°C, the activation pressure was 10 MPa, the gas volume space velocity was 0.3 L / h / L Cat, and the activation time was 7 hours.

[0059] 2-aminomethylcyclopentylamine was obtained under the conditions of reaction temperature of 180°C, reaction pressure of 1MPa, 1-amino-2-cyanocyclopentene space velocity of 0.5L / h / LCat, and molar ratio of hydrogen to 1-amino-2-cyanocyclopentene of 3:1. According to gas chromatography analysis, the reaction conversion rate was 100.0% and the product selectivity was 99.9%. After the catalyst was continuously operated for 2300h, according to gas chromatography analysis, the reaction conversion rate was 99.6% and the product selectivity was 99.1%.

[0060] Comparative Example 1

[0061] Compared with Example 1, other conditions remained unchanged. During the catalyst activation process, the CO content was reduced to 30 ppm. According to gas chromatography analysis, the reaction conversion rate was 100%, and the product selectivity was 90.5%. After the catalyst was continuously operated for 1000 hours, according to gas chromatography analysis, the reaction conversion rate was 95.6%, and the product selectivity was 89.1%.

[0062] Comparative Example 2

[0063] Compared with Example 1, other conditions remained unchanged. During the catalyst activation process, the CO content increased to 240 ppm. According to gas chromatography analysis, the reaction conversion rate was 92.4% and the product selectivity was 99.3%. After the catalyst was continuously operated for 1000 hours, according to gas chromatography analysis, the reaction conversion rate was 85.2% and the product selectivity was 95.5%.

[0064] Comparative Example 3

[0065] Compared with Example 1, other conditions remain unchanged, silicon dioxide is used as a carrier instead of YSiO3 carrier, and the reaction conversion rate is 90.4% and the product selectivity is 96.7% according to gas chromatography analysis. After the catalyst is continuously operated for 800 hours, the reaction conversion rate is 80.5% and the product selectivity is 91.3% according to gas chromatography analysis.

[0066] Comparative Example 4

[0067] Compared with Example 1, other conditions remained unchanged, Gd2O3 was not added to the active components, and the reaction conversion rate was 96.5% and the product selectivity was 97.0% according to gas chromatography analysis. After the catalyst was continuously operated for 600 hours, the reaction conversion rate was 90.5% and the product selectivity was 87.3% according to gas chromatography analysis.

[0068] Comparative Example 5

[0069] Compared with Example 1, other conditions remained unchanged, V2O5 was not added to the active components, and the reaction conversion rate was 100% and the product selectivity was 92.4% according to gas chromatography analysis. After the catalyst was continuously operated for 500 hours, the reaction conversion rate was 92.5% and the product selectivity was 85.7% according to gas chromatography analysis.

[0070] Example 2

[0071] (1) Preparation of 5wt%Ag2O-1.8wt%V2O5-0.1wt%Gd2O3 / YSiO3

[0072] 200 g of silicon dioxide and 18.6 g of yttrium hydroxide were added to a mortar and mixed evenly. After grinding and sieving, a 120-mesh mixture was obtained. Then, the mixture was transferred to a crucible, dried at 120°C for 10 h, and then calcined in air at 1000°C for 4 h (heating rate: 3°C / min; heating rate refers to the temperature rising from room temperature to the final temperature at a certain rate per minute) to obtain YSiO3 white powder (X-ray diffraction analysis showed that the purity of YSiO3 was higher than 98%). After tableting, a 3*3 mm columnar carrier was obtained. The specific surface area of ​​the carrier was 200 m 2 / g, the pore volume is 0.5ml / g, and the average pore diameter is 100nm.

[0073] According to the content composition of the catalyst, 100 g of the above-mentioned carrier was immersed in an aqueous solution containing 13.64 g of anhydrous silver nitrate, 13.99 g of ammonium metavanadate and 0.16 g of gadolinium nitrate hexahydrate by an equal volume impregnation method. After adsorption equilibrium was reached, it was dried at 120°C for 10 h and then calcined in air at 350°C for 7 h to obtain a catalyst precursor of 5wt% Ag2O-1.8wt% V2O5 -0.1wt% Gd2O3 / YSiO3.

[0074] (2) Evaluation of catalyst

[0075] The catalyst was evaluated by a continuous fixed bed process, and 100 ml of hydrogenation catalyst was added to the fixed bed reactor. Hydrogen containing 200 ppm CO was used for activation, the activation temperature was 80°C, the activation pressure was 8 MPa, the gas volume space velocity was 0.4 L / h / L Cat, and the activation time was 7 h.

[0076] 2-aminomethylcyclopentylamine was obtained under the conditions of reaction temperature of 170°C, reaction pressure of 2MPa, 1-amino-2-cyanocyclopentene space velocity of 0.8L / h / LCat, and molar ratio of hydrogen to 1-amino-2-cyanocyclopentene of 4:1. According to gas chromatography analysis, the reaction conversion rate was 100.0% and the product selectivity was 99.5%. After the catalyst was continuously operated for 2400h, according to gas chromatography analysis, the reaction conversion rate was 99.5% and the product selectivity was 99.2%.

[0077] Example 3

[0078] (1) Preparation of 7wt%Ag2O-1.5wt%V2O5-0.3wt%Gd2O3 / YSiO3

[0079] 200 g of silicon dioxide and 6 g of yttrium carbonate were added to a mortar and mixed evenly. After grinding and sieving, a 140-mesh mixture was obtained. Then, the mixture was transferred to a crucible, dried at 130°C for 8 h, and then calcined in air at 750°C for 8 h (heating rate: 3°C / min; heating rate refers to the temperature rising from room temperature to the final temperature at a certain rate per minute) to obtain YSiO3 white powder (X-ray diffraction analysis shows that the purity of YSiO3 is higher than 98%). After tableting, a 3*3 mm columnar carrier with a specific surface area of ​​400 m 2 / g, the pore volume is 0.6ml / g, and the average pore diameter is 150nm.

[0080] According to the content composition of the catalyst, 100 g of the above-mentioned carrier was immersed in an aqueous solution containing 19.10 g of anhydrous silver nitrate, 11.66 g of ammonium metavanadate and 0.48 g of gadolinium nitrate hexahydrate by an equal volume impregnation method. After adsorption equilibrium was reached, it was dried at 130°C for 8 h and then calcined in air at 400°C for 6 h to obtain a catalyst precursor of 7wt% Ag2O-1.5wt% V2O5 -0.3wt% Gd2O3 / YSiO3.

[0081] (2) Evaluation of catalyst

[0082] The catalyst was evaluated using a continuous fixed bed process, and 100 ml of hydrogenation catalyst was added to the fixed bed reactor. Hydrogen containing 50 ppm CO was used for activation, the activation temperature was 90°C, the activation pressure was 7 MPa, the gas volume space velocity was 0.1 L / h / L Cat, and the activation time was 5 h.

[0083] 2-aminomethylcyclopentylamine was obtained under the conditions of reaction temperature of 150°C, reaction pressure of 0.5MPa, 1-amino-2-cyanocyclopentene space velocity of 1.2L / h / LCat, and molar ratio of hydrogen to 1-amino-2-cyanocyclopentene of 5:1. According to gas chromatography analysis, the reaction conversion rate was 100.0% and the product selectivity was 99.0%. After the catalyst was continuously operated for 2350h, according to gas chromatography analysis, the reaction conversion rate was 99.7% and the product selectivity was 99.4%.

[0084] Example 4

[0085] (1) Preparation of 10wt% Ag2O-1.0wt% V2O5-0.1wt% Gd2O3 / YSiO3

[0086] 200 g of silicon dioxide and 73.5 g of yttrium oxalate nonahydrate were added to a mortar and mixed evenly. After grinding and sieving, a 160-mesh mixture was obtained. Then, the mixture was transferred to a crucible, dried at 150°C for 6 h, and then calcined in air at 850°C for 6 h (heating rate: 3°C / min; heating rate refers to the temperature rising from room temperature to the final temperature at a certain rate per minute) to obtain YSiO3 white powder (X-ray diffraction analysis shows that the purity of YSiO3 is higher than 98%). After tableting, a 3*3 mm columnar carrier with a specific surface area of ​​100 m 2 / g, the pore volume is 0.8ml / g, and the average pore diameter is 180nm.

[0087] According to the content composition of the catalyst, 100 g of the above-mentioned carrier was immersed in an aqueous solution containing 27.28 g of anhydrous silver nitrate, 7.77 g of ammonium metavanadate and 0.08 g of gadolinium nitrate hexahydrate by an equal volume impregnation method. After adsorption equilibrium was reached, it was dried at 150°C for 6 hours and then calcined in air at 450°C for 5 hours to obtain a catalyst precursor 10wt% Ag2O-1.0wt% V2O5 -0.1wt% Gd2O3 / YSiO3.

[0088] (2) Evaluation of catalyst

[0089] The catalyst was evaluated using a continuous fixed bed process, and 100 ml of hydrogenation catalyst was added to the fixed bed reactor. Hydrogen containing 120 ppm CO was used for activation, the activation temperature was 110°C, the activation pressure was 5 MPa, the gas volume space velocity was 0.6 L / h / L Cat, and the activation time was 12 h.

[0090] 2-aminomethylcyclopentylamine was obtained under the conditions of reaction temperature of 190°C, reaction pressure of 3MPa, 1-amino-2-cyanocyclopentene space velocity of 1.6L / h / LCat, and molar ratio of hydrogen to 1-amino-2-cyanocyclopentene of 6:1. According to gas chromatography analysis, the reaction conversion rate was 100.0% and the product selectivity was 99.6%. After the catalyst was continuously operated for 2200h, according to gas chromatography analysis, the reaction conversion rate was 99.6% and the product selectivity was 99.2%.

[0091] Example 5

[0092] (1) Preparation of 12wt%Ag2O-0.5wt%V2O5-1.0wt%Gd2O3 / YSiO3

[0093] 200 g of silicon dioxide and 14.0 g of yttrium hydroxide were added to a mortar and mixed evenly. After grinding and sieving, a 200-mesh mixture was obtained. Then, the mixture was transferred to a crucible, dried at 170°C for 5 h, and then calcined in air at 800°C for 7 h (heating rate: 3°C / min; heating rate refers to the temperature rising from room temperature to the final temperature at a certain rate per minute) to obtain YSiO3 white powder (X-ray diffraction analysis showed that the purity of YSiO3 was higher than 98%). After tableting, a 3*3 mm columnar carrier was obtained. The specific surface area of ​​the carrier was 350 m 2 / g, the pore volume is 0.7ml / g, and the average pore diameter is 200nm.

[0094] According to the content composition of the catalyst, 100 g of the above-mentioned carrier was immersed in an aqueous solution containing 32.74 g of anhydrous silver nitrate, 3.89 g of ammonium metavanadate and 1.61 g of gadolinium nitrate hexahydrate by an equal volume impregnation method. After adsorption equilibrium was reached, it was dried at 170°C for 5 h and then calcined in air at 500°C for 4 h to obtain a catalyst precursor 12wt% Ag2O-0.5wt% V2O5 -1.0wt% Gd2O3 / YSiO3.

[0095] (2) Evaluation of catalyst

[0096] The catalyst was evaluated using a continuous fixed bed process, and 100 ml of hydrogenation catalyst was added to the fixed bed reactor. Hydrogen containing 150 ppm CO was used for activation, the activation temperature was 130°C, the activation pressure was 3 MPa, the gas volume space velocity was 0.8 L / h / L Cat, and the activation time was 10 h.

[0097] 2-aminomethylcyclopentylamine was obtained by the reaction at a reaction temperature of 200°C, a reaction pressure of 4MPa, a 1-amino-2-cyanocyclopentene space velocity of 1.8L / h / LCat, and a molar ratio of hydrogen to 1-amino-2-cyanocyclopentene of 10:1. According to gas chromatography analysis, the reaction conversion rate was 100.0% and the product selectivity was 99.8%. After the catalyst was continuously operated for 2250h, according to gas chromatography analysis, the reaction conversion rate was 99.7% and the product selectivity was 99.3%.

[0098] Example 6

[0099] (1) Preparation of 15wt%Ag2O-0.1wt%V2O5-0.8wt%Gd2O3 / YSiO3

[0100] 200 g of silicon dioxide and 11.9 g of yttrium carbonate were added to a mortar and mixed evenly. After grinding and sieving, a 120-mesh mixture was obtained. Then, the mixture was transferred to a crucible, dried at 200°C for 4 h, and then calcined in air at 700°C for 9 h (heating rate: 3°C / min; heating rate refers to the temperature rising from room temperature to the final temperature at a certain rate per minute) to obtain YSiO3 white powder (X-ray diffraction analysis showed that the purity of YSiO3 was higher than 98%). After tableting, a 3*3 mm columnar carrier was obtained. The specific surface area of ​​the carrier was 300 m 2 / g, the pore volume is 0.5ml / g, and the average pore diameter is 120nm.

[0101] According to the content composition of the catalyst, 100 g of the above-mentioned carrier was immersed in an aqueous solution containing 40.93 g of anhydrous silver nitrate, 0.78 g of ammonium metavanadate and 1.28 g of gadolinium nitrate hexahydrate by an equal volume impregnation method. After adsorption equilibrium was reached, it was dried at 200°C for 4 hours and then calcined in air at 600°C for 2 hours to obtain a catalyst precursor 15wt% Ag2O-0.1wt% V2O5-0.8wt% Gd2O3 / YSiO3.

[0102] (2) Evaluation of catalyst

[0103] The catalyst was evaluated using a continuous fixed bed process, and 100 ml of hydrogenation catalyst was added to the fixed bed reactor. Hydrogen containing 150 ppm CO was used for activation, the activation temperature was 130°C, the activation pressure was 3 MPa, the gas volume space velocity was 0.8 L / h / L Cat, and the activation time was 10 h.

[0104] 2-aminomethylcyclopentylamine was obtained under the conditions of reaction temperature of 220°C, reaction pressure of 5MPa, 1-amino-2-cyanocyclopentene space velocity of 2.0L / h / LCat, and molar ratio of hydrogen to 1-amino-2-cyanocyclopentene of 8:1. According to gas chromatography analysis, the reaction conversion rate was 100.0% and the product selectivity was 99.4%. After the catalyst was continuously operated for 2100h, according to gas chromatography analysis, the reaction conversion rate was 99.5% and the product selectivity was 99.1%.

[0105] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as limiting the present invention. Those skilled in the art will appreciate that, under the guidance of this specification, some modifications or adjustments may be made to the present invention. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A method for preparing 2-aminomethylcyclopentylamine, characterized in that: The method comprises the steps of using 1-amino-2-cyanocyclopentene as a raw material, reacting with a hydrogenation catalyst having YSiO3 as a carrier and Ag2O, V5O2 and Gd2O3 as active components to obtain 2-aminomethylcyclopentylamine; the hydrogenation catalyst further comprises the step of using hydrogen containing ppm-level CO for activation, and the CO content in the activation step is 50-200 ppm.

2. The preparation method according to claim 1, characterized in that: The active components of the hydrogenation catalyst are supported on a carrier; based on the weight of the carrier, the mass content of each active component is: Ag2O 2-15wt%; V5O2 0.1-2wt%; Gd2O3 0.05-1wt%.

3. The preparation method according to claim 2, characterized in that: The active components of the hydrogenation catalyst are supported on a carrier; based on the weight of the carrier, the mass content of each active component is: Ag2O 5-10wt%; V5O2 0.5-1.5wt%; Gd2O3 0.1-0.5wt%.

4. The preparation method according to any one of claims 1 to 3, characterized in that: In the carrier YSiO3, the molar ratio of Si to Y element is 1:0.01-1:0.

05.

5. The preparation method according to claim 4, characterized in that: In the carrier YSiO3, the molar ratio of Si to Y element is 1:0.02-1:0.

04.

6. The preparation method according to any one of claims 1 to 3, characterized in that: The specific surface area of ​​the carrier is 100 m 2 / g-400m 2 / g; pore volume is 0.3ml / g-0.8ml / g; average pore diameter is 50-200nm.

7. The preparation method according to claim 6, characterized in that: The specific surface area of ​​the carrier is 200m 2 / g-300m 2 / g; pore volume is 0.5ml / g-0.6ml / g; average pore diameter is 100-150nm.

8. The preparation method according to any one of claims 1 to 3, characterized in that: The preparation method of the hydrogenation catalyst comprises the following steps: a) preparing a YSiO3 carrier: uniformly mixing a yttrium-containing compound with silicon dioxide, grinding, sieving, drying, calcining, and molding to obtain a carrier; b) preparing the catalyst: the carrier obtained in step a) is immersed in an aqueous solution containing soluble silver salt, vanadium salt and gadolinium salt, dried after adsorption equilibrium is reached, and calcined to obtain a catalyst precursor.

9. The preparation method according to claim 8, characterized in that: In the step a), the drying temperature is 100-200° C.; the drying time is 4-12 hours; the roasting temperature is 600-1000° C., and the roasting time is 4-10 hours.

10. The preparation method according to claim 9, characterized in that: In the step a), the drying temperature is 120-150° C., the drying time is 6-10 hours, the roasting temperature is 750-850° C., and the roasting time is 6-8 hours.

11. The preparation method according to claim 8, characterized in that: In the step b), the impregnation is equal volume impregnation.

12. The preparation method according to claim 8, characterized in that: In the step b), the drying temperature is 100-200° C.; the drying time is 4-12 hours; the roasting temperature is 300-600° C., and the roasting time is 2-8 hours.

13. The preparation method according to claim 12, characterized in that: In the step b), the drying temperature is 120-150° C., the drying time is 6-10 hours, the roasting temperature is 400-500° C., and the roasting time is 4-6 hours.

14. The preparation method according to any one of claims 1 to 3, characterized in that: The activation comprises adding 100 mL of hydrogenation catalyst into a fixed bed reactor, the activation temperature is 50-150° C., and the activation time is 5-15 hours.

15. The preparation method according to claim 14, characterized in that: The activation temperature is 70-130°C; the activation time is 7-12h.

16. The preparation method according to claim 15, characterized in that: The activation temperature is 90-110°C; the activation time is 8-10h.

17. The preparation method according to claim 14, characterized in that: The CO content in the activation step is 80-180 ppm.

18. The preparation method according to claim 17, characterized in that: The CO content in the activation step is 120-150 ppm.

19. The preparation method according to claim 14, characterized in that: The activation pressure is 1-10MPa; the volume space velocity of the gas is 0.1-1L / h / L Cat.

20. The preparation method according to claim 19, characterized in that: The activation pressure is 3-8MPa; the volume space velocity of the gas is 0.3-0.8L / h / L Cat.

21. The preparation method according to claim 20, characterized in that: The activation pressure is 5-7MPa; the volume space velocity of the gas is 0.4-0.6L / h / L Cat.

22. The preparation method according to claim 1, characterized in that: The reaction temperature is 150-220°C; the reaction pressure is 0.5-5MPa.

23. The preparation method according to claim 22, characterized in that: The reaction temperature is 170-200°C; the reaction pressure is 1-4MPa.

24. The preparation method according to claim 23, characterized in that: The reaction temperature is 180-190°C; the reaction pressure is 2-3MPa.

25. The preparation method according to claim 22, characterized in that: The space velocity of 1-amino-2-cyanocyclopentene is 0.5-2 L / h / L Cat; the molar ratio of hydrogen to 1-amino-2-cyanocyclopentene is 3:1-10:

1.

26. The preparation method according to claim 25, characterized in that: The space velocity of 1-amino-2-cyanocyclopentene is 0.8-1.8 L / h / L Cat; the molar ratio of hydrogen to 1-amino-2-cyanocyclopentene is 4:1-8:

1.

27. The preparation method according to claim 26, characterized in that: The space velocity of 1-amino-2-cyanocyclopentene is 1.2-1.6 L / h / L Cat; the molar ratio of hydrogen to 1-amino-2-cyanocyclopentene is 5:1-6:1.