CN109678732B - Method for continuously producing 5-amino-1-pentanol - Google Patents
Method for continuously producing 5-amino-1-pentanol Download PDFInfo
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Abstract
The invention discloses a method for continuously producing 5-amino-1-pentanol, which comprises the step of carrying out continuous reductive amination reaction on a mixed reaction system containing a dihydropyran hydrate, ammonia water and a supported nickel-based catalyst in a fixed bed reactor to prepare the 5-amino-1-pentanol. The invention takes cheap and easily obtained dihydropyran hydrate and ammonia water as raw materials, and takes supported non-noble metal nickel as a catalyst in a fixed bed reactor to realize the continuous production of 5-amino-1-pentanol at lower reaction temperature and hydrogen pressure, and the reaction product and the catalyst are directly separated in the reaction process without separate filtration or centrifugal treatment, so the catalyst has good service life stability, simple operation and process, obviously improved production efficiency, reduced production cost and convenient large-scale industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a method for continuously producing 5-amino-1-pentanol.
Background
Amino alcohol is an important bifunctional compound containing hydroxyl and amino in a molecule, is widely used for synthesis of medicines and pesticides, and is also commonly used as an organic synthesis block. In addition, amino alcohols are structural motifs of a variety of natural product molecules, and generally have biological activity and high medicinal value. For example, Manzamine a is an alkaloid with good antitumor and antifungal activities, and the starting material for its synthesis is 5-amino-1-pentanol. With the popularization and application of the Manzamine A medicine, the demand of 5-amino-1-pentanol is more and more increased.
The amino alcohol is usually prepared by a Grignard reagent addition method, a halohydrin amino substitution method, an amino acid (ester) reduction method, or the like. The methods have the disadvantages of low atom economy due to the generation of a large amount of waste, high price and low availability of raw materials, and are mostly batch preparation methods with low production efficiency.
For example, chinese patent CN104974049A discloses a method for preparing 1, 5-amino alcohol by addition reaction of grignard reagent and tetrahydrofuran using imine as raw material, wherein a large amount of grignard reagent and iodo compound are added during the reaction, resulting in high production cost and large amount of waste.
For another example, there is a document (fine chemical intermediates, 2014, 44(6), 40-42) reporting a method of preparing 5-chloropentanol intermediate by monochloro substitution of concentrated hydrochloric acid using 1, 5-pentanediol as a raw material, and separating the intermediate and then reacting the separated intermediate with ammonia gas to obtain 5-amino-1-pentanol. The method has the advantages that the price of the raw material of the 1, 5-pentanediol is high, a large amount of concentrated hydrochloric acid needs to be added in the reaction process, a large amount of NaOH needs to be neutralized in the post-treatment process, a large amount of waste is generated, and only moderate (73.2%) yield of the amino alcohol is obtained.
For another example, chinese patent CN106810459A discloses a method for preparing amino alcohol by continuous hydroamination using dihydric alcohol as a raw material in a fixed bed reactor, but the reaction conditions are severe and the activity and selectivity are low. For example, in the hydroamination of 1, 6-hexanediol at 160 ℃ and 8MPa H2, the conversion of 1, 6-hexanediol and the selectivity for aminohexanol are at most only 73% and 43%, respectively.
For example, chinese patent CN108947851A discloses a method for preparing 5-amino-1-pentanol under mild reaction conditions by using cheap and easily available dihydropyran as a raw material and performing two-step reactions of hydration and ammoniation, but the method is a batch tank reaction, the reaction product and the catalyst need to be centrifuged or filtered, the production efficiency is low, the catalyst is complicated to reuse and operate, the effect is poor, and the production cost is high.
Obviously, the prior art method also has the problems of high production cost, unclean and efficient production process, harsh reaction conditions, low yield of target products and the like, and is not beneficial to large-scale industrial production. Therefore, development of a novel method for producing 5-amino-1-pentanol with high efficiency and low cost is urgently needed.
Disclosure of Invention
The main object of the present invention is to provide a process for the continuous production of 5-amino-1-pentanol overcoming the drawbacks of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for continuously producing 5-amino-1-pentanol, which comprises the step of carrying out continuous reductive amination reaction on a mixed reaction system containing a dihydropyran hydrate, ammonia water and a supported nickel-based catalyst in a fixed bed reactor to prepare the 5-amino-1-pentanol.
In some embodiments, a mixed reaction system comprising dihydropyran hydrate, aqueous ammonia, and a supported nickel-based catalyst is subjected to a continuous reductive amination reaction in a fixed bed reactor in a hydrogen atmosphere to produce 5-amino-1-pentanol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention can continuously and efficiently produce 5-amino-1-pentanol, which takes cheap and easily obtained dihydropyran hydrate and ammonia water as raw materials to carry out continuous reductive amination reaction in a fixed bed reactor to produce 5-amino-1-pentanol, thereby realizing continuous flow production at lower reaction temperature and hydrogen pressure, having cheap and easily obtained production raw materials and simple and efficient reaction process.
(2) The supported non-noble metal nickel is used as a catalyst to realize the continuous stable reductive amination of the dihydropyran hydrate and the ammonia water to produce the 5-amino-1-pentanol, and the catalyst has low cost and small investment. The reaction product and the catalyst are directly separated in the reaction process, separate filtration or centrifugal treatment is not needed, the catalyst has good service life stability and simple operation and process, the production efficiency is obviously improved, the production cost is reduced, the large-scale industrial production is convenient, and the economic benefit is obviously improved.
(3) The method has mild reaction conditions, simple and safe operation, obviously reduces the investment of production devices and production energy consumption, and is convenient for realizing industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a diagram showing the chromatographic analysis of 5-amino-1-pentanol product obtained in example 6 of the present invention with 1, 2-pentanediol as an internal standard after dissolving in ethanol.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides a method for continuously producing 5-amino-1-pentanol, which comprises the step of carrying out continuous reductive amination reaction on a mixed reaction system containing a dihydropyran hydrate, ammonia water and a supported nickel-based catalyst in a fixed bed reactor to prepare the 5-amino-1-pentanol.
In some embodiments, a mixed reaction system comprising dihydropyran hydrate, aqueous ammonia, and a supported nickel-based catalyst is subjected to a continuous reductive amination reaction in a fixed bed reactor in a hydrogen atmosphere to produce 5-amino-1-pentanol.
The reaction formula is as follows:
in some preferred embodiments, the temperature of the reductive amination reaction is 60-120 ℃, the pressure is 1-4 MPa, the volume ratio of hydrogen to the reaction solution (the mixed solution of dihydropyran hydrate and ammonia) is 600-1800: 1, and the feeding volume space velocity is 4-30 h-1。
In some embodiments, the preparation of the dihydropyran hydrate comprises: reacting dihydropyran with water at 60-140 ℃ for 0.5-20h in a protective atmosphere to obtain a dihydropyran hydrate.
In some preferred embodiments, the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere such as argon.
In some preferred embodiments, the mass ratio of the dihydropyran to the water is 1: 2-9.
In some preferred embodiments, the pressure of the reaction is 0.1 to 3 MPa.
In some embodiments, the mass ratio of the dihydropyran hydrate to the ammonia water is 1: 0.5-2.
In some embodiments, the supported nickel-based catalyst includes a primary active component, a promoter, and a support.
In some more preferred embodiments, the primary active component is selected from Ni.
In some preferred embodiments, the promoter comprises any one or a combination of two or more of Co, Cu, Fe, Zn, Mn, Mo, Ru, Re, La, Y and Ce.
In some more preferred embodiments, the support comprises Al2O3、SiO2、ZrO2、TiO2And MgO.
In some more preferred embodiments, the content of the main active component accounts for 2-35 wt%, preferably 5-25 wt% of the total mass of the supported nickel-based catalyst, and the content of the auxiliary agent accounts for 0.1-10 wt% of the total mass of the supported nickel-based catalyst.
The invention provides a method for continuously preparing 5-amino-1-pentanol by taking a dihydropyran hydrate and ammonia water as raw materials through a fixed bed reactor, wherein the dihydropyran hydrate and the ammonia water are mixed according to a certain proportion and then pumped into the reactor through a pump, and amination reaction is carried out in the presence of a supported Ni-based catalyst and H2. The product is mainly 5-amino-1-pentanol through Agilent 7890A/5975C GC-MS combined analysis, and the byproducts comprise 1, 5-pentanediol, imine, dihydropyran hydrate dimer and the like. The product was quantitatively analyzed by Agilent 7890A gas chromatography with hydrogen Flame Ionization Detector (FID), HP-5 capillary chromatography column, and 1, 2-pentanediol as internal standard.
The technical solutions of the present invention will be described in further detail with reference to several preferred embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The conditions used in the following examples may be further adjusted as necessary, and the conditions used in the conventional experiments are not generally indicated.
Example 1: preparation of dihydropyran hydrate
Weighing dihydropyran and deionized water according to the mass ratio of 1: 2-1: 9, adding the dihydropyran and the deionized water into a 2L reaction kettle, sealing the kettle, and adding N2Pressurizing to 0.1-3MPa after replacement, raising the temperature to 60-140 ℃ under rapid stirring, reacting at the temperature for 0.5-20h, cooling, and collecting reaction liquid for later use, wherein the table 1 shows dihydropyran hydrates prepared under different conditions.
TABLE 1 preparation of dihydropyran hydrate under different conditions and amination Performance thereof
Example 2: preparation of supported nickel-based catalyst
Adding water to dissolve a certain mass of nickel salt and metal additive salt to prepare a solution, adding the dried carrier, stirring into a uniform mud shape, dipping for 12h at normal temperature, drying for 12h at 110 ℃, and roasting for 3h at 500 ℃. The tablets were sieved to 20-40 mesh catalyst particles and 2mL (2.4g) was packed in a fixed bed reactor. Finally, the temperature is raised to 450 ℃ in the hydrogen atmosphere (the flow rate is 80-100mL/min) for reduction for 4h, and the activated catalyst is obtained, and the composition of the catalyst is shown in Table 2.
TABLE 2 catalyst composition and performance of amination of dihydropyran hydrates
Example 3: performance of different catalysts in catalyzing amination reaction of dihydropyran hydrate and ammonia water
The dihydropyrane hydrate 3 prepared in the example 1 and 25% strong ammonia water are evenly mixed according to the mass ratio of 1: 1 and pumped into a reactor at the reaction temperature of 90 ℃ and H2Pressure 3MPa, H2The volume ratio of the reaction solution to the reaction solution is 1200 and the space velocity of the feeding volume is 10h-1The amination reaction performance of different supported Ni-based catalysts is researched under the condition, and a sample after 6h of stabilization is taken for gas chromatography analysis. From the results of Table 2, it can be seen that the yield of the target 5-amino-1-pentanol is between 79 and 93%, which indicates that the catalyst synthesized by the present invention can efficiently catalyze the amination reaction of dihydropyran hydrate and ammonia.
Example 4: amination Performance of dihydropyran hydrates under different conditions
Uniformly mixing a dihydropyran hydrate and 25% concentrated ammonia water according to the mass ratio of 1: 1, pumping the mixture into a reactor at the reaction temperature of 90 ℃ and H2Pressure 3MPa, H2The volume ratio of the reaction solution to the reaction solution is 1200 and the space velocity of the feeding volume is 10h-1The amination performance of the No. 5 catalyst is studied under the condition, and a sample after 6 hours of stabilization is taken for gas chromatography analysis. It can be seen from the results of Table 1 that the dihydropyran hydrate synthesized by the reaction of low temperature for a long time and high temperature for a short time is advantageous for obtaining 5-amino-1-pentanol in a high yield (> 86%) within the selected range of the ratio of dihydropyran to water and the ranges of the hydration temperature and the reaction time.
Example 5: amination reaction performance of dihydropyran hydrate under different reaction conditions
The dihydropyran hydrate 3 prepared in the example 1 and 25% strong ammonia water are uniformly mixed according to a certain mass ratio, and pumped into a reactor, and the proportion of the dihydropyran hydrate and the ammonia water, the reaction temperature and the H content are researched by using No. 5 catalyst2Pressure, H2The volume ratio of the reaction solution and the feeding volume airspeed influence the amination reaction performance, and a sample after 6 hours of stabilization is taken for gas chromatographyThe results of the analysis are shown in Table 3. Therefore, under the mild reaction conditions of the invention, such as temperature not higher than 120 ℃ and pressure not higher than 4MPa, the high yield (> 87%) of the 5-amino-1-pentanol can be conveniently synthesized by adjusting the ratio of the dihydropyran hydrate to the ammonia water and the feeding volume space velocity.
TABLE 3.5 amination Performance of the catalyst under different reaction conditions
Example 6: continuous reaction stability study of catalyst
The dihydropyrane hydrate 3 prepared in the example 1 and 25% strong ammonia water are evenly mixed according to the mass ratio of 1: 1 and pumped into a reactor at the reaction temperature of 90 ℃ and H2Pressure 2MPa, H2The volume ratio of the reaction solution to the reaction solution is 1200 and the space velocity of the feeding volume is 10h-1The continuous reaction stability of the No. 5 catalyst is studied under the condition, and samples are taken every 6 to 12 hours for gas chromatography analysis. From the results of Table 4, it can be seen that the catalyst maintained good stability and the yield of 5-amino-1-pentanol was maintained around 92% after 120 hours of operation. Distilling ammonia from the collected reaction solution (absorbing the distilled ammonia gas with sulfuric acid), distilling under reduced pressure after ammonia distillation is finished, collecting 83-85 deg.C fraction, dissolving the product in ethanol, analyzing purity by gas chromatography with 1, 2-pentanediol as internal standard to reach 97%, and obtaining chromatogram shown in figure 1.
TABLE 4.5 amination Performance of catalyst No. 4 at various reaction times
| Reaction time (h) | Dihydropyran conversion (%) | Yield (%) of 5-amino-1-pentanol |
| 6 | 100 | 92.6 |
| 12 | 100 | 91.8 |
| 24 | 100 | 91.9 |
| 36 | 100 | 92.3 |
| 48 | 100 | 92.0 |
| 60 | 100 | 91.6 |
| 72 | 100 | 91.8 |
| 84 | 100 | 91.5 |
| 96 | 100 | 92.3 |
| 108 | 100 | 91.6 |
| 120 | 100 | 92.1 |
Comparative example 1
20g of dihydropyrane hydrate 3 prepared in example 1 and 20g of 25% concentrated aqueous ammonia were weighed into a 100mL reaction vessel, 0.4g of active catalyst 5 activated under the same conditions as in example 2 and stored in a sealed state under an atmosphere of H2 was added, the vessel was sealed, and H was introduced2After 3 times of replacement, H is2The pressure is increased to 3MPa, the temperature is increased to 90 ℃ for reaction for 4H, and H is supplemented in the reaction process2Maintaining the pressure constant, cooling with cooling water after the reaction is finished, centrifugally separating the reaction liquid, and analyzing the conversion rate of the dihydropyrane to be 100% and the yield of the 5-amino-1-pentanol to be 91.8% by using gas chromatography of the supernatant.
Washing the centrifugally separated catalyst with deionized water, centrifugally separating, pouring out washing water, circularly washing for 3 times, washing the reaction solution prepared from 40g of dihydropyran hydrate 3 and 25% of concentrated ammonia water in a mass ratio of 1: 1 into a reaction kettle, carrying out amination reaction according to the conditions, and analyzing results to show that the yield of the 5-amino-1-pentanol is greatly reduced to 63.0%. The recycling is repeated, and the yield of the 5-amino-1-pentanol is reduced to 34.1 percent.
The catalyst was thus tested for its recyclability in a batch reactor. The results show that the batch kettle type reaction has the disadvantages of complicated operation, low efficiency and poor effect in catalyst recycling, and the product produced on the unit mass of the catalyst is far lower than that produced on a fixed bed.
Therefore, the invention takes the dihydropyran hydrate and the ammonia water which are cheap and easy to obtain as raw materials, and takes the supported non-noble metal nickel as the catalyst in the fixed bed reactor, thereby realizing the continuous production of the 5-amino-1-pentanol at lower reaction temperature and H2 pressure, directly separating the reaction product from the catalyst in the reaction process, needing no separate filtration or centrifugal treatment, having good service life stability of the catalyst, simple operation and process, obviously improving the production efficiency, reducing the production cost and being convenient for large-scale industrial production.
In addition, the inventor also carries out corresponding experiments by using other raw materials and other process conditions listed above instead of various raw materials and corresponding process conditions in the examples 1 to 6, and the contents to be verified are similar to the products in the examples 1 to 6. Therefore, the contents of the verification of each example are not described herein one by one, and only examples 1 to 6 are used as representatives to describe the excellent points of the present invention.
It should be understood that the above describes only some embodiments of the present invention and that various other changes and modifications may be affected therein by one of ordinary skill in the related art without departing from the scope or spirit of the invention.
Claims (4)
1. A process for the continuous production of 5-amino-1-pentanol, characterized by comprising: in hydrogen atmosphere, enabling a mixed reaction system containing a dihydropyran hydrate, ammonia water and a supported nickel-based catalyst to perform continuous reductive amination reaction in a fixed bed reactor to prepare 5-amino-1-pentanol;
the temperature of the reductive amination reaction is 60-120 ℃, the pressure is 1-4 MPa, the volume ratio of hydrogen to a mixed solution of a dihydropyran hydrate and ammonia water is 600-1800: 1, the mass ratio of the dihydropyran hydrate to the ammonia water is 1: 0.5-2, and the feeding volume airspeed is 4-30 h-1；
The supported nickel-based catalyst comprises a carrier, 2-35 wt% of a main active component and 0.1-10 wt% of an auxiliary agent, wherein the main active component is Ni, the auxiliary agent is selected from any one or a combination of more than two of Co, Cu, Fe, Zn, Mn, Mo, Ru, Re, La, Y and Ce, and the carrier is selected from Al2O3、SiO2、ZrO2、TiO2And MgO.
2. The method for continuously producing 5-amino-1-pentanol according to claim 1, wherein the preparation of the dihydropyran hydrate comprises: reacting dihydropyran and water in a mass ratio of 1: 2-9 in a protective atmosphere at a pressure of 0.1-3MPa and a temperature of 60-140 ℃ for 0.5-20h to obtain a dihydropyran hydrate.
3. The process for the continuous production of 5-amino-1-pentanol according to claim 2, characterized in that: the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere.
4. The process for the continuous production of 5-amino-1-pentanol according to claim 1, characterized in that: the content of the main active component accounts for 5-25% of the total mass of the supported nickel-based catalyst.
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