Method for preparing 1, 4-butanediamine by one step through butyrolactam and utilization method of 1, 4-butanediamine rectifying still residues
Butyraclamide is recovered by negative pressure distillation of the 1,4-butylene diamine stillage residue, and one-step method of ammonia dehydration catalytic hydrogenation is used to prepare 1,4-butylene diamine, which solves the problem of difficult and high cost of processing residual liquid in the stillage, and achieves the reuse of resources and the reduction of production costs.
Patent Information
- Application Number
- CN202411819421.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-10
- Publication Date
- 2025-03-28
AI Technical Summary
During the distillation and purification process of 1,4-butanediamine, the residual liquid in the still kettle is difficult to handle and costly, and an efficient and economical treatment method is urgently needed.
By distilling the residue of the 1,4-butanediamine still kettle with a purity of >95.0%, the butyracene recovery solution was recovered, and 1,4-butanediamine was prepared by a one-step method of ammonia dehydration catalytic hydrogenation using the butyracene raw material.
It realizes efficient recycling and reuse of butylactam, reduces solid waste treatment, reduces production costs, and improves the product yield and economic benefits of 1,4-butanediamine.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of resource recycling, and in particular to a method for preparing 1,4-butanediamine from butyrolactam in one step and a method for utilizing the residue from a distillation still of 1,4-butanediamine. Background Art
[0002] 1,4-Butanediamine (also known as putrescine) is an important chemical intermediate and biochemical precursor. It can be used in pharmaceutical and biochemical research, preparation of surfactants and agricultural chemicals. It is an important raw material for synthesizing high-quality engineering plastics polybutylene adipamide (commonly known as nylon 46, abbreviated as PA46) and 1,4-butanediisocyanate (BDI), and has broad market prospects.
[0003] The main production method of butanediamine is chemical synthesis at present: acrylonitrile and hydrocyanic acid are used as raw materials to synthesize succinonitrile in the presence of an alkaline catalyst, and succinonitrile is hydrogenated to obtain butanediamine hydrogenated liquid. The hydrogenated liquid is then subjected to light removal, decoking, and vacuum distillation purification to obtain a higher purity 1,4-butanediamine product.
[0004] When using this method to prepare 1,4-butanediamine products, the study found that when distilling and purifying 1,4-butanediamine products, the residual liquid in the distillation kettle is mainly composed of diamine (~1%), butyrolactam (~65%) and heavy components (~30%), and after continuous enrichment, it is difficult to handle this part of the residual liquid in the distillation kettle, and the processing cost is high.
[0005] Therefore, there is an urgent need for a method for efficiently and economically treating the distillation residue of 1,4-butanediamine. Summary of the invention
[0006] In order to solve the above technical problems, the present invention provides a method for preparing 1,4-butanediamine from butyrolactam in one step and a method for utilizing the residue from the distillation of 1,4-butanediamine. The present invention finds that by performing negative pressure distillation on the residue from the distillation of 1,4-butanediamine, a butyrolactam recovery liquid with a purity of more than 95.0% can be obtained, and 1,4-butanediamine can be prepared from the butyrolactam recovery liquid, thereby achieving resource recycling and reducing the amount of solid waste treatment.
[0007] To achieve this object, the present invention adopts the following technical solutions:
[0008] In a first aspect, the present invention provides a method for preparing 1,4-butanediamine from butyrolactam in one step, the method comprising: introducing ammonia, hydrogen and butyrolactam raw materials into a fixed bed reactor containing a catalyst to react and obtain a reaction material containing 1,4-butanediamine.
[0009] It is worth noting that there is no relevant report on the synthesis of 1,4-butanediamine using butyrolactam as raw material, and the existing preparation of hexanediamine from caprolactam often needs to be completed by a two-step method, and there are a series of problems such as low purification efficiency, short catalyst life, low raw material conversion rate, poor target product synthesis selectivity, and complex process flow in the middle, and there are differences in physical and chemical properties between caprolactam and butyrolactam, which is difficult to directly convert. In this regard, the present invention uses a method for preparing 1,4-butanediamine by ammonia dehydration catalytic hydrogenation one-step method for butyrolactam raw materials, integrating butyrolactam ammoniation and hydrogenation, which not only significantly reduces energy loss, realizes the resource recycling of distillation kettle residues, and makes the reaction safer and more stable, effectively improves product selectivity and process safety, and becomes one of the important means to reduce the production cost of 1,4-butanediamine and improve the product yield and economic benefits of 1,4-butanediamine. And while being able to reduce the cost of handling the residual liquid of the waste distillation kettle of butanediamine, it also improves the yield of the target product and reduces production costs.
[0010] Preferably, the catalyst comprises a carrier, an active component and an auxiliary agent; the active component and the auxiliary agent are loaded on the carrier.
[0011] The present invention preferably uses a catalyst containing an auxiliary agent in the catalyst, wherein the auxiliary agent can cooperate with the active component to significantly improve the selectivity of 1,4-butanediamine.
[0012] Preferably, the active component is nickel.
[0013] Preferably, the auxiliary agent comprises any one of potassium, zinc, potassium oxide or zinc oxide, or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of potassium and zinc, a combination of potassium oxide and zinc, a combination of potassium and potassium oxide, a combination of zinc oxide and zinc, and a combination of potassium and zinc oxide.
[0014] Preferably, the particle size of the catalyst is 10 to 100 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0015] Preferably, the pore volume of the catalyst is 0.1 to 0.5 mL / g, for example, it may be 0.1 mL / g, 0.15 mL / g, 0.19 mL / g, 0.24 mL / g, 0.28 mL / g, 0.33 mL / g, 0.37 mL / g, 0.42 mL / g, 0.46 mL / g or 0.5 mL / g, but is not limited to the listed values, and other values not listed within the range are also applicable.
[0016] Preferably, the nickel content in the catalyst is 3-5%, for example, it can be 3%, 3.1%, 3.2%, 3.3%, 3.5%, 3.8%, 4%, 4.2%, 4.3%, 4.5% or 5%, but is not limited to the listed values, and other unlisted values within this range are also applicable.
[0017] Preferably, the content of the additive in the catalyst is 0.1-1%, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc., but is not limited to the listed values, and other values not listed within this range are also applicable.
[0018] The present invention further prefers that the content of the auxiliary agent in the catalyst is within the above range. When the content of the auxiliary agent is too high, it is easy to cause the conversion rate of butyrolactam to decrease, and the selectivity to decrease accordingly. When the content of the auxiliary agent is too low, the selectivity of the catalysis is also reduced.
[0019] Preferably, the mass ratio of nickel to additive in the catalyst is 0.1 to 10:1, for example, it can be 0.1:1, 1.2:1, 2.3:1, 3.4:1, 4.5:1, 5.6:1, 6.7:1, 7.8:1, 8.9:1 or 10:1, but is not limited to the listed values, and other unlisted values within this range are also applicable.
[0020] Preferably, the catalyst is in the shape of any one of spheres, rods or cakes, or a combination of at least two of them, wherein typical but non-limiting combinations are a combination of spheres and rods, a combination of cakes and rods, and a combination of spheres and cakes.
[0021] Preferably, the support comprises Al2O3 and / or SiO2.
[0022] Preferably, the specific surface area of the carrier is 100 to 2500 m 2 / g, for example, it can be 100m 2 / g, 367m 2 / g, 634m 2 / g、900m 2 / g, 1167m 2 / g、1434m 2 / g、1700m 2 / g, 1967m 2 / g, 2234m 2 / g or 2500m 2 / g, etc., but are not limited to the listed values, and other values not listed within the range are also applicable.
[0023] Preferably, the pore volume of the carrier is 0.5 to 3.0 mL / g, for example, 0.5 mL / g, 0.8 mL / g, 1.1 mL / g, 1.4 mL / g, 1.7 mL / g, 1.9 mL / g, 2.2 mL / g, 2.5 mL / g, 2.8 mL / g or 3.0 mL / g, but is not limited to the listed values, and other values not listed within the range are also applicable.
[0024] Preferably, the preparation method of the catalyst comprises:
[0025] The mixed metal nickel salt, the auxiliary metal oxide source and acetone are mixed to obtain an active component acetone solution.
[0026] The carrier and the active component acetone solution are mixed for impregnation, and then dried, calcined and activated in sequence to obtain the catalyst.
[0027] Preferably, the metal nickel salt comprises nickel nitrate and / or nickel chloride.
[0028] Preferably, the auxiliary metal oxide source includes any one of potassium chloride, potassium carbonate, zinc chloride or zinc nitrate, or a combination of at least two of them, wherein typical but non-limiting combinations are a combination of potassium chloride and potassium carbonate, a combination of zinc chloride and potassium carbonate, a combination of potassium chloride and zinc chloride, and a combination of zinc nitrate and potassium carbonate.
[0029] Preferably, the mass fraction of the metal nickel salt in the active component acetone solution is 0.1-10%, for example, it can be 0.1%, 1.2%, 2.3%, 3.4%, 4.5%, 5.6%, 6.7%, 7.8%, 8.9% or 10%, etc., but is not limited to the listed values, and other values not listed within this range are also applicable.
[0030] Preferably, the mass fraction of the auxiliary metal oxide source in the active component acetone solution is 0.01-2%, for example, it can be 0.01%, 0.12%, 0.23%, 0.34%, 0.45%, 0.56%, 0.67%, 0.78%, 0.89%, 1%, 1.2%, 1.5%, 1.8% or 2.0%, etc., but is not limited to the listed values, and other values not listed within the range are also applicable.
[0031] Preferably, the mass ratio of the active component acetone solution to the carrier in the impregnation is 1 to 3:1, for example, it can be 1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0032] Preferably, the immersion temperature is 20-50°C, for example, it can be 20°C, 24°C, 27°C, 30°C, 34°C, 37°C, 40°C, 44°C, 47°C or 50°C, but is not limited to the listed values, and other values not listed within the range are equally applicable. The soaking time is 10-20h, for example, it can be 10h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, but is not limited to the listed values, and other values not listed within the range are equally applicable.
[0033] Preferably, the drying temperature is 80-140°C, for example, it can be 80°C, 87°C, 94°C, 100°C, 107°C, 114°C, 120°C, 127°C, 134°C or 140°C, but is not limited to the listed values, and other values not listed in this range are equally applicable. The drying time is 5-10h, for example, it can be 5h, 5.6h, 6.2h, 6.7h, 7.3h, 7.8h, 8.4h, 8.9h, 9.5h or 10h, but is not limited to the listed values, and other values not listed in this range are equally applicable.
[0034] Preferably, the calcination temperature is 200-600°C, for example, it can be 200°C, 245°C, 289°C, 334°C, 378°C, 423°C, 467°C, 512°C, 556°C or 600°C, but is not limited to the listed values. Other unlisted values within this range are also applicable, preferably 300-500°C.
[0035] Preferably, the calcination time is 1 to 10 h, for example, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, but is not limited to the listed values, and other values not listed within the range are also applicable.
[0036] Preferably, the calcination is carried out in a protective atmosphere.
[0037] Preferably, the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two of them, wherein typical but non-limiting combinations are a combination of nitrogen and argon, a combination of helium and argon, and a combination of nitrogen and helium.
[0038] Preferably, the activation comprises: activating the calcined catalyst in a hydrogen atmosphere.
[0039] Preferably, the activation temperature is 200-600°C, for example, it can be 200°C, 245°C, 289°C, 334°C, 378°C, 423°C, 467°C, 512°C, 556°C or 600°C, but is not limited to the listed values, and other values not listed within the range are equally applicable. The time is 0.5-12h, for example, it can be 0.5h, 1.8h, 3.1h, 4.4h, 5.7h, 6.9h, 8.2h, 9.5h, 10.8h or 12h, but is not limited to the listed values, and other values not listed within the range are equally applicable.
[0040] Preferably, the space velocity of hydrogen in the activation is 20 to 4000 h -1 , for example, it can be 20h -1 、463h -1 、905h -1 , 1347h -1 、1789h -1 、2232h -1 、2674h -1 、3116h -1 、3558h -1 or 4000h -1 The above values are not limited to the above values, and other values not listed in the above values are also applicable.
[0041] Preferably, the reaction comprises an ammonialysis ring-opening dehydration reaction and a hydrogenation reaction.
[0042] Preferably, the reaction temperature is 100-500°C, for example, it can be 100°C, 145°C, 189°C, 234°C, 278°C, 323°C, 367°C, 412°C, 456°C or 500°C, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0043] It is worth noting that the key to the direct one-step preparation of 1,4-butanediamine in the present invention lies in the catalyst and the reaction temperature. The present invention further preferably controls the reaction temperature within the above range, which can better match the catalyst, and the selectivity and conversion rate of the one-step reaction are high.
[0044] Preferably, the reaction pressure is 0.1-10 MPa, for example, 0.1 MPa, 1.2 MPa, 2.3 MPa, 3.4 MPa, 4.5 MPa, 5.6 MPa, 6.7 MPa, 7.8 MPa, 8.9 MPa or 10 MPa, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0045] When the reaction pressure of the present invention is too high or too low, the conversion rate of butyrolactam and the selectivity of 1,4-butanediamine may both decrease.
[0046] Preferably, the space velocity ratio of ammonia to hydrogen is 0.8 to 1.2:1, for example, it can be 0.8:1, 0.82:1, 0.85:1, 0.86:1, 0.88:1, 0.89:1, 0.9:1, 1.0:1, 1.02:1, 1.05:1, 1.08:1, 1.1:1, 1.12:1, 1.15:1 or 1.2:1, etc.
[0047] Preferably, the weight hourly space velocity of butyrolactam is 0.1 to 30 h -1 , for example, it can be 0.1h -1 , 3.5h -1 , 6.8h -1 , 10.1h -1 、13.4h -1 、16.8h -1 , 20.1h -1 , 23.4h -1 , 26.7h -1 or 30h -1 The above values are not limited to the above values, and other values not listed in the above values are also applicable.
[0048] Preferably, the volume space velocity of ammonia is 50 to 100 h -1 , for example, it can be 50h -1 , 56h -1 , 62h -1 , 67h -1 , 73h -1 , 78h -1 , 84h -1 、89h -1 , 95h -1 or 100h -1 The above values are not limited to the above values, and other values not listed in the above values are also applicable.
[0049] Preferably, the hydrogen volume space velocity in the reaction is 50 to 100 h -1 , for example, it can be 50h -1 , 56h -1 , 62h -1 , 67h -1 , 73h -1 , 78h -1 , 84h -1 、89h -1 , 95h -1 or 100h -1The above values are not limited to the above values, and other values not listed in the above values are also applicable.
[0050] In the present invention, when the hydrogen space velocity is high, over-hydrogenation occurs, the conversion rate of butyrolactam is not significantly affected, but the hydrogenation selectivity of 1,4-butanediamine is poor; when the hydrogen space velocity is low, the conversion rate of butyrolactam is not significantly affected, but the hydrogenation effect is insufficient, and the hydrogenation selectivity of 1,4-butanediamine is poor.
[0051] Preferably, the method further comprises: separating and purifying the reaction product to obtain a high-purity 1,4-butanediamine product.
[0052] The present invention separates and purifies the 1,4-butanediamine product in the reaction material. The reaction product includes 1,4-butanediamine, tetrahydropyrrole, a small amount of polymer, water and unreacted butyrolactam.
[0053] The purity of the high-purity 1,4-butanediamine product of the present invention is greater than or equal to 99.9%.
[0054] Preferably, the separation and purification process comprises light removal, decoking and vacuum distillation performed in sequence.
[0055] In a second aspect, the present invention provides a method for utilizing the residue from the distillation of 1,4-butanediamine, the method comprising the method for preparing 1,4-butanediamine from butyrolactam in one step as described in the first aspect, wherein the source of the butyrolactam raw material comprises: butyrolactam recovery liquid obtained by vacuum distillation of the residue from the distillation of 1,4-butanediamine.
[0056] The method provided by the present invention uses the distillation kettle residue generated in the traditional production process of preparing 1,4-butanediamine by hydrogenating 1,4-succinonitrile as a raw material, obtains butyrolactam recovery liquid by negative pressure distillation, and re-prepares 1,4-butanediamine by a one-step method through ammonia dehydration catalytic hydrogenation reaction on the butyrolactam recovery liquid. The by-product butyrolactam generated in the production process of 1,4-butanediamine can be returned to the preparation route of 1,4-butanediamine, and 1,4-butanediamine can be prepared by a one-step method, thereby reducing the cost of treating the waste butanediamine distillation kettle residue, while improving the yield of the target product and reducing the production cost.
[0057] Preferably, the purity of butyrolactam in the butyrolactam recovery liquid is greater than 99.50wt%, for example, it can be 99.51wt%, 99.52wt%, 99.53wt%, 99.54wt%, 99.58wt%, 99.60wt%, 99.65wt%, 99.70wt%, 99.75wt%, 99.80wt% or 99.85wt%, etc.
[0058] The present invention has no particular limitation on the drying in the above process. Any drying device and method known to those skilled in the art can be used, and can also be adjusted according to the actual process, for example, it can be air drying, vacuum drying, oven drying or freeze drying, or a combination of different methods.
[0059] Compared with the prior art, the present invention has at least the following beneficial effects:
[0060] (1) The method for preparing 1,4-butanediamine from butyrolactam in one step provided by the present invention adopts a fixed bed reactor for one-step preparation, and the final conversion rate and yield of 1,4-butanediamine are both high. Under preferred conditions, the conversion rate of butyrolactam is as high as 98.3% or more, the selectivity of 1,4-butanediamine is as high as 95.3% or more, and the amount of solid waste reduced by butyrolactam raw materials is as high as 98.1% or more. The method has low energy consumption and broad application prospects.
[0061] (2) The method for utilizing the residue from the distillation kettle of 1,4-butanediamine provided by the present invention obtains a butyrolactam recovery liquid by negative pressure distillation, and the butyrolactam recovery liquid is re-prepared into a 1,4-butanediamine product by a one-step method through ammonia decomposition and catalytic hydrogenation, thereby reducing the cost of treating the residue from the distillation kettle of discarded butanediamine and further improving the yield of the target product, reducing the discharge of three wastes, being green and environmentally friendly, being suitable for industrial production, and having good market prospects. DETAILED DESCRIPTION
[0062] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.
[0063] Catalyst A
[0064] Mix nickel nitrate, zinc oxide and acetone to obtain an active component acetone solution; the mass fraction of nickel nitrate in the active component acetone solution is 5%, and the mass fraction of zinc oxide is 0.5%;
[0065] According to the active component acetone solution and carrier (specific surface area 2000m 3 The mass ratio of the carrier and the active component acetone solution was 1.5:1, and the mixed carrier and the active component were immersed in acetone solution at 30 ° C for 10 h, and then dried at 100 ° C for 6 h, calcined at 500 ° C in nitrogen atmosphere for 5 h, and finally heated at a space velocity of 1500 h -1 Hydrogen was introduced, the mixture was activated at 350° C. for 4 h, and the catalyst A was obtained after crushing and screening.
[0066] Catalyst B
[0067] Mixing nickel chloride, zinc nitrate and acetone to obtain an active component acetone solution; the mass fraction of nickel chloride in the active component acetone solution is 3.7%, and the mass fraction of zinc nitrate is 1%;
[0068] According to the active component acetone solution and carrier (specific surface area 1500m 3 / g, spherical Al2O3 with a pore volume of 25mL / g and a diameter of 2mm) was used in a mass ratio of 2:1, the mixed carrier and the active component acetone solution were impregnated at 40℃ for 6h, then dried at 120℃ for 5h, calcined at 600℃ in a nitrogen atmosphere for 8h, and finally calcined at a space velocity of 1000h -1 Hydrogen was introduced, the mixture was activated at 600° C. for 4 h, and the catalyst B was obtained after crushing and screening.
[0069] Catalyst C
[0070] Mix nickel nitrate, potassium chloride and acetone to obtain an active component acetone solution; the mass fraction of nickel nitrate in the active component acetone solution is 2%, and the mass fraction of potassium chloride is 0.27%;
[0071] According to the active component acetone solution and carrier (specific surface area 500m 3 / g, pore volume 1mL / g of rod-shaped SiO2, radius 0.5mm, height 2mm) mass ratio of 3:1, the mixed carrier and active component acetone solution were immersed at 25℃ for 4h, and then dried at 80℃ for 5h, calcined at 200℃ in nitrogen atmosphere for 4h, and finally heated at a space velocity of 500h -1 Hydrogen was introduced, and the mixture was activated at 200° C. for 4 h, and then crushed and sieved to obtain the catalyst C.
[0072] Catalyst D
[0073] Mix nickel nitrate, potassium carbonate and acetone to obtain an active component acetone solution; the mass fraction of nickel nitrate in the active component acetone solution is 2.67%, and the mass fraction of potassium carbonate is 1%;
[0074] According to the active component acetone solution and carrier (specific surface area 1000m 3 The mass ratio of the carrier and the active component acetone solution was 1.2:1, and the mixed carrier and the active component were immersed in acetone solution at 35 ° C for 10 h, and then dried at 80 ° C for 5 h, calcined at 200 ° C in a nitrogen atmosphere for 10 h, and finally heated at a space velocity of 100 h. -1 Hydrogen was introduced, and the mixture was activated at 600° C. for 0.5 h. The catalyst D was obtained after crushing and screening.
[0075] Catalyst E
[0076] The only difference between catalyst E and catalyst A is that zinc oxide is not added, and the rest is the same as catalyst A, which will not be repeated here.
[0077] Catalyst F
[0078] The only difference between Catalyst F and Catalyst A is that the mass fraction of zinc oxide in the acetone solution of the active component is 1.5%, and the rest is the same as Catalyst A, which will not be repeated here.
[0079] Catalyst G
[0080] The only difference between Catalyst G and Catalyst A is that nickel nitrate in the active component acetone solution is replaced by cobalt nitrate, and the rest is the same as Catalyst A, which will not be repeated here.
[0081] The ICP method was used to detect the nickel and additive contents in the catalyst, and the particle size analysis and BET methods were used to detect the particle size and pore volume of the catalyst.
[0082] The test results of the above catalysts are shown in Table 1 below.
[0083] Table 1
[0084]
[0085] Example 1
[0086] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine, and the utilization method comprises the following steps:
[0087] The butyrolactam recovery liquid obtained by vacuum distillation of the 1,4-butanediamine distillation still residue is the butyrolactam raw material, and the purity of butyrolactam in the butyrolactam raw material is 99.8%;
[0088] Catalyst A was added to the fixed bed reactor, and the packing density of catalyst A was 0.87 g / mL;
[0089] Ammonia, hydrogen and butyrolactam raw materials are introduced into a fixed bed reactor containing a catalyst for reaction at a temperature of 300°C, a pressure of 5 MPa, and a weight hourly space velocity of butyrolactam of 10 h -1 The volumetric space velocity of ammonia is 60h -1 The volumetric space velocity of hydrogen is 58h -1 , obtaining a reaction material containing 1,4-butanediamine;
[0090] The reaction product is subjected to light removal, decoking, and vacuum distillation, and then analyzed by gas chromatography to obtain 1,4-butanediamine.
[0091] Example 2
[0092] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine, and the utilization method comprises the following steps:
[0093] The butyrolactam recovery liquid obtained by vacuum distillation of the 1,4-butanediamine distillation still residue is the butyrolactam raw material, and the purity of butyrolactam in the butyrolactam raw material is 99.8wt%;
[0094] Catalyst B was added to the fixed bed reactor, and the packing density of catalyst B was 0.88 g / mL;
[0095] Ammonia, hydrogen and butyrolactam raw materials are introduced into a fixed bed reactor containing a catalyst for reaction at a temperature of 500°C, a pressure of 6 MPa, and a weight hourly space velocity of butyrolactam of 20 h -1 The volumetric space velocity of ammonia is 80h -1 , the volume space velocity of hydrogen is 80h -1 , obtaining a reaction material containing 1,4-butanediamine;
[0096] The reaction product is subjected to light removal, decoking, and vacuum distillation, and then analyzed by gas chromatography to obtain 1,4-butanediamine.
[0097] Example 3
[0098] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine, and the utilization method comprises the following steps:
[0099] The butyrolactam recovery liquid obtained by vacuum distillation of the 1,4-butanediamine distillation still residue is the butyrolactam raw material, and the purity of butyrolactam in the butyrolactam raw material is 99.8wt%;
[0100] Catalyst C was added into the fixed bed reactor, and the packing density of catalyst C was 0.85 g / mL;
[0101] Ammonia, hydrogen and butyrolactam raw materials are introduced into a fixed bed reactor containing a catalyst for reaction at a temperature of 200°C, a pressure of 3 MPa, and a weight hourly space velocity of butyrolactam of 10 h -1 The volumetric space velocity of ammonia is 50h -1 The volumetric space velocity of hydrogen is 50h -1 , obtaining a reaction material containing 1,4-butanediamine;
[0102] The reaction product is subjected to light removal, decoking, and vacuum distillation, and then analyzed by gas chromatography to obtain 1,4-butanediamine.
[0103] Example 4
[0104] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine, and the utilization method comprises the following steps:
[0105] The butyrolactam recovery liquid obtained by vacuum distillation of the 1,4-butanediamine distillation still residue is the butyrolactam raw material, and the purity of butyrolactam in the butyrolactam raw material is 99.8wt%;
[0106] Catalyst D was added to the fixed bed reactor, and the packing density of catalyst D was 0.86 g / mL;
[0107] Ammonia, hydrogen and butyrolactam raw materials are introduced into a fixed bed reactor containing a catalyst for reaction at a temperature of 250°C, a pressure of 8 MPa, and a weight hourly space velocity of butyrolactam of 15 h -1 The volumetric space velocity of ammonia is 60h -1 The volumetric space velocity of hydrogen is 60h -1 , obtaining a reaction material containing 1,4-butanediamine;
[0108] The reaction product is subjected to light removal, decoking, and vacuum distillation, and then analyzed by gas chromatography to obtain 1,4-butanediamine.
[0109] Example 5
[0110] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The utilization method is the same as that of Embodiment 1 except that catalyst A is replaced by catalyst E, and will not be described in detail here.
[0111] Example 6
[0112] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The utilization method is the same as that of Embodiment 1 except that catalyst A is replaced by catalyst F, and thus will not be described in detail herein.
[0113] Example 7
[0114] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The utilization method is the same as that of Embodiment 1 except that catalyst A is replaced by catalyst G, and thus will not be described in detail herein.
[0115] Example 8
[0116] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The method is the same as that of Embodiment 1 except that the reaction temperature is 180° C., and will not be described in detail here.
[0117] Example 9
[0118] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The method is the same as that of Embodiment 1 except that the reaction temperature is 600° C., and will not be described in detail here.
[0119] Example 10
[0120] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The method is the same as that of Embodiment 1 except that the reaction pressure is 15 MPa, and thus will not be described in detail.
[0121] Embodiment 11
[0122] This embodiment provides a method for utilizing the distillation still residue of 1,4-butanediamine. The method is the same as that of Embodiment 1 except that the reaction pressure is 0.05 MPa, and thus will not be described in detail.
[0123] Example 12
[0124] This embodiment provides a method for utilizing the residue from the distillation of 1,4-butanediamine. The method removes hydrogen at a volume space velocity of 70 h -1 Except for this, the rest are the same as those in Example 1 and will not be described again.
[0125] Example 13
[0126] This embodiment provides a method for utilizing the residue from the distillation of 1,4-butanediamine. The method removes hydrogen at a volume space velocity of 40 h -1 Except for this, the rest are the same as those in Example 1 and will not be described again.
[0127] Comparative Example 1
[0128] This comparative example provides a method for utilizing the distillation still residue of 1,4-butanediamine. The utilization method is the same as Example 1 except that the reaction is carried out in two steps, and will not be described in detail here.
[0129] Specifically, the two-step reaction process includes:
[0130] A nitrate molecular sieve catalyst was added to the fixed bed reactor of ammonolysis, and ammonia and butyrolactam raw materials were introduced into the fixed bed reactor containing the catalyst to react at a temperature of 400°C, a pressure of 1 MPa, and a weight hourly space velocity of butyrolactam of 10 h -1 The volumetric space velocity of ammonia is 60h -1 , to obtain 4-aminobutyronitrile;
[0131] Subsequently, a molecular sieve loaded with nickel and cobalt was added as a catalyst in the hydrogenation fixed bed, and hydrogen and 4-aminobutyronitrile were introduced into the fixed bed reactor containing the catalyst to react at a temperature of 300°C, a pressure of 5 MPa, and a weight hourly space velocity of 4-aminobutyronitrile of 10 h -1 The volumetric space velocity of hydrogen is 60h -1, hydrogenation is performed to obtain a hydrogenated liquid containing 1,4-butanediamine. After the hydrogenated liquid is subjected to light removal, decoking, and vacuum distillation, pure 1,4-butanediamine can be obtained through gas chromatography analysis.
[0132] Comparative Example 2
[0133] This comparative example provides a method for utilizing the distillation still residue of 1,4-butanediamine. The utilization method is the same as Example 1 except that no catalyst is added, and will not be described in detail here.
[0134] Test method: The above reaction was evaluated for 10 hours, and the post-reaction material was subjected to gas chromatography analysis. The separated high-purity 1,4-butanediamine was subjected to gas chromatography analysis, and the conversion rate of butyrolactam and the selectivity of 1,4-butanediamine were calculated according to the following formulas. At the same time, the amount of solid waste reduction was evaluated according to the proportion of 1,4-butanediamine in the original 1,4-butanediamine distillation kettle residue.
[0135]
[0136] The test results of the above embodiments and comparative examples are shown in Table 1.
[0137] Table 1
[0138]
[0139] From Table 1, we can see the following points:
[0140] (1) It can be seen from Examples 1 to 4 that the method for preparing 1,4-butanediamine from butyrolactam in one step provided by the present invention can achieve a one-step method for preparing 1,4-butanediamine from butyrolactam, wherein the conversion rate of butyrolactam is as high as 98.3% or more, the selectivity of 1,4-butanediamine is as high as 95.3% or more, and the amount of solid waste reduced from butyrolactam raw materials is as high as 98.1% or more, and the application prospect is broad;
[0141] (2) It can be seen from Example 1 and Examples 5 to 6 that in Example 1, the catalyst A containing an appropriate amount of additive is used. Compared with Examples 5 to 6 in which no additive is contained or the additive content is relatively high, the conversion rate of butyrolactam in Example 1 is 99.2%, and the selectivity of 1,4-butanediamine is 97.6%, while the conversion rates of butyrolactam in Examples 5 to 6 are only 90.2% and 88.3%, respectively, and the selectivity of 1,4-butanediamine is only 85.6% and 81.6%, respectively. This shows that the present invention can further improve the yield of 1,4-butanediamine by preferably adding an additive to the catalyst and controlling the content of the additive within a reasonable range;
[0142] (3) It can be seen from Example 1 and Examples 5 to 6 that the catalyst A containing an appropriate amount of additives is used in Example 1. Compared with Examples 5 to 6 in which no additives are contained or the additive content is relatively high, the conversion rate of butyrolactam in Example 1 is 99.2%, and the selectivity of 1,4-butanediamine is 97.6%, while the conversion rates of butyrolactam in Examples 5 to 6 are only 90.2% and 88.3%, respectively, and the selectivity of 1,4-butanediamine is only 85.6% and 81.6%, respectively. This shows that the present invention can further improve the yield of 1,4-butanediamine by preferably adding an additive to the catalyst and controlling the content of the additive within a reasonable range;
[0143] (4) It can be seen from Example 1 and Example 7 that the nickel-based catalyst A used in Example 1 has a conversion rate of butyrolactam of 99.2% and a selectivity of 1,4-butanediamine of 97.6% compared to the cobalt-based catalyst G used in Example 7, while the conversion rate of butyrolactam in Example 7 is only 80.5% and the selectivity of 1,4-butanediamine is only 79.8%. Catalyst G is a cobalt-based catalyst. Compared with nickel-based catalysts, the ability of cobalt-based catalysts to undergo ammonolysis is relatively weak, which will lead to a significant decrease in the conversion rate of butyrolactam and a corresponding decrease in the selectivity of catalytic hydrogenation of butanediamine. This shows that the present invention can further improve the yield of 1,4-butanediamine by preferably using a nickel-based catalyst;
[0144] (5) It can be seen from Example 1 and Examples 8 to 13 that the temperature, pressure and air velocity during the reaction process have a great influence on the conversion rate and yield of the reaction. When the temperature is low, the conversion rate of butyrolactam will be greatly reduced, and the selectivity of catalytic hydrogenation of diamine will be greatly reduced. When the temperature is high, the conversion rate of butyrolactam will decrease slightly, and the selectivity of catalytic hydrogenation of diamine will decrease slightly accordingly. When the reaction pressure is too high, similar to the case of high temperature, the conversion rate of butyrolactam will decrease slightly, and the selectivity of catalytic hydrogenation of diamine will decrease slightly accordingly. When the reaction pressure is too low, the conversion rate of butyrolactam will decrease significantly, and the selectivity of catalytic hydrogenation of diamine will be significantly poor. When the hydrogen air velocity is high, over-hydrogenation will occur, and the conversion rate of butyrolactam will not be significantly affected, but the selectivity of diamine hydrogenation will be poor. When the hydrogen air velocity is low, the conversion rate of butyrolactam will not be significantly affected, but the hydrogenation effect is insufficient, and the selectivity of diamine hydrogenation will be poor.
[0145] (6) It can be seen from Example 1 and Comparative Examples 1 to 3 that the conversion rate and yield of Comparative Example 1, which adopts a two-step reaction, are not as good as those of Example 1. In Comparative Example 2, no catalyst is added, and the conversion rate and yield of the reaction are very low, which is difficult to meet industrial requirements.
[0146] The present invention illustrates the detailed features of the present invention through the above embodiments, but the present invention is not limited to the above detailed features, that is, it does not mean that the present invention must rely on the above detailed features to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of the technical features selected by the present invention, addition of auxiliary technical features, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A method for preparing 1,4-butanediamine from butyrolactam in one step, characterized in that: The method comprises: introducing ammonia, hydrogen and butyrolactam raw materials into a fixed bed reactor filled with a catalyst to react and obtain a reaction material containing 1,4-butanediamine.
2. The method according to claim 1, characterized in that The catalyst comprises a carrier, an active component and an auxiliary agent; the active component and the auxiliary agent are loaded on the carrier; Preferably, the active component is nickel; Preferably, the auxiliary agent includes any one of potassium, zinc, potassium oxide or zinc oxide, or a combination of at least two thereof.
3. The method according to claim 1 or 2, characterized in that: The particle size of the catalyst is 10 to 100 μm; Preferably, the pore volume of the catalyst is 0.1 to 0.5 mL / g; Preferably, the nickel content in the catalyst is 3-5%; Preferably, the content of the auxiliary agent in the catalyst is 0.1 to 1%; Preferably, the mass ratio of nickel to additive in the catalyst is 0.1 to 10:1; Preferably, the catalyst is in the shape of any one of sphere, rod or cake, or a combination of at least two of them.
4. The method according to any one of claims 1 to 3, characterized in that: The carrier comprises Al2O3 and / or SiO2; Preferably, the specific surface area of the carrier is 100 to 2500 m 2 / g; Preferably, the pore volume of the carrier is 0.5 to 3.0 mL / g.
5. The method according to any one of claims 1 to 4, characterized in that: The preparation method of the catalyst comprises: Mixing a metal nickel salt, an auxiliary metal oxide source and acetone to obtain an active component acetone solution; The carrier and the active component acetone solution are mixed for impregnation, and then dried, calcined and activated in sequence to obtain the catalyst.
6. The method according to claim 5, characterized in that The metal nickel salt includes nickel nitrate and / or nickel chloride; Preferably, the auxiliary metal oxide source includes any one or a combination of at least two of potassium chloride, potassium carbonate, zinc chloride or zinc nitrate; Preferably, the mass fraction of the metal nickel salt in the active component acetone solution is 0.1-10%; Preferably, the mass fraction of the auxiliary metal oxide source in the active component acetone solution is 0.01-2%.
7. The method according to any one of claims 1 to 6, characterized in that: The mass ratio of the active component acetone solution to the carrier in the impregnation is 1 to 3:1; Preferably, the immersion temperature is 20 to 50°C and the immersion time is 10 to 20 hours; Preferably, the drying temperature is 80-140°C and the drying time is 5-10 hours; Preferably, the calcination temperature is 200-600°C, preferably 300-500°C; Preferably, the calcination time is 1 to 10 hours; Preferably, the calcination is carried out in a protective atmosphere; Preferably, the protective atmosphere includes any one of nitrogen, argon or helium, or a combination of at least two of them.
8. The method according to any one of claims 1 to 7, characterized in that: The activation comprises: activating the calcined catalyst in a hydrogen atmosphere; Preferably, the activation temperature is 200-600°C and the activation time is 0.5-12h; Preferably, the space velocity of hydrogen in the activation is 20 to 4000 h -1 .
9. The method according to any one of claims 1 to 8, characterized in that: The reaction includes an ammonia decomposition ring-opening dehydration reaction and a hydrogenation reaction; Preferably, the reaction temperature is 200-500°C; Preferably, the reaction pressure is 0.1-10 MPa; Preferably, the space velocity ratio of ammonia to hydrogen is 0.8 to 1.2:1; Preferably, the weight hourly space velocity of butyrolactam is 0.1 to 30 h -1 ; Preferably, the volume space velocity of ammonia is 50 to 100 h -1 ; Preferably, the hydrogen volume space velocity in the reaction is 50 to 100 h -1 ; Preferably, the method further comprises: separating and purifying the reaction product to obtain a high-purity 1,4-butanediamine product; Preferably, the separation and purification process comprises light removal, decoking and vacuum distillation performed in sequence.
10. A method for utilizing the residue from the distillation of 1,4-butanediamine, characterized in that: The utilization method comprises the method for preparing 1,4-butanediamine from butyrolactam in one step according to any one of claims 1 to 9, characterized in that the source of the butyrolactam raw material comprises: butyrolactam recovery liquid obtained by vacuum distillation of the 1,4-butanediamine distillation still residue; Preferably, the purity of butyrolactam in the butyrolactam recovery liquid is greater than 99.50 wt%.