WO2022110930A1 - Procédé d'ammoximation de la macrocycloalcanone - Google Patents

Procédé d'ammoximation de la macrocycloalcanone Download PDF

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Publication number
WO2022110930A1
WO2022110930A1 PCT/CN2021/114318 CN2021114318W WO2022110930A1 WO 2022110930 A1 WO2022110930 A1 WO 2022110930A1 CN 2021114318 W CN2021114318 W CN 2021114318W WO 2022110930 A1 WO2022110930 A1 WO 2022110930A1
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acid
macrocycloalkanone
hydrogen peroxide
mass
ammoximation
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PCT/CN2021/114318
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English (en)
Chinese (zh)
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冯传密
吴昊
史文涛
杨光
靳权
龙滢
王聪
刘新伟
王元平
杨克俭
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中国天辰工程有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • the invention belongs to the field of fine chemical industry and new material preparation, in particular to a method for ammoximation of macrocycloalkanone.
  • the macrocycloalkanone ammoximation method is a key process for preparing long carbon chain nylon polymers. After long carbon chain nylon is processed and formed, its product properties can meet the characteristics of existing PA66, PA6, PE and PP materials. Nylon material has low water absorption, excellent dimensional stability, easy processing and high product accuracy. In addition, the long carbon chain nylon material has high resistance to medium corrosion, oil resistance, chemical resistance, and is safe to use.
  • the traditional process of macrocycloalkanone oximation reaction is macrocycloalkanone, hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine phosphate.
  • Hydroxylamine is an important intermediate raw material for the reaction, and hydroxylamine is released by adjusting the alkalinity of the reaction.
  • Patent DE-OS2111792 describes a process for the preparation of a mixture of cyclohexanone oxime and cyclododecanone oxime by reacting a ketone with hydroxylamine in the form of hydroxylamine sulfate, the reaction technique being carried out in two steps.
  • the pH value is adjusted to 3-4.5, the reaction temperature is 80-90 °C, and the reaction is performed for a specific time under this condition;
  • the second step the pH value is adjusted to 5-6, the reaction temperature is 90-110 °C, and the under conditions for a specific time.
  • this technology is very beneficial to control the ability of iron ions to decompose hydroxylamine and reduce the loss of hydroxylamine raw materials.
  • the shortcoming of this technique is also very obvious.
  • this technique is still not the oximation technique of Laxi liquid method, a large amount of by-product ammonium sulfate is inevitably produced, which is unfriendly to the environment.
  • this reaction system has relatively fine regulation of temperature and regulation of pH value, small operation flexibility, and complicated chain and control of industrialized devices, which will inevitably increase the production cost of products and reduce the competitiveness of products.
  • Titanium-containing molecular sieve catalysts are widely used in the oximation of caprolactam cyclohexanone. In 1983, Taramasso and his collaborators successfully synthesized titanium-containing molecular sieve catalysts for the first time. This catalyst is TS-1.
  • Patent EP0496385 describes the oximation reaction of carbonyl compounds in the liquid phase, and the system is a green ammoximation reaction process. Although the system uses various carbonyl compounds such as cyclohexanone, cyclododecanone and acetophenone alone, the advantages of this system are not clearly stated.
  • Patent CN200410010449 describes the use of Ti-MWW as a catalyst to catalyze the ammoximation reaction of cycloalkanone, but only the ammoximation reaction of cyclohexanone is introduced in the examples, and the yield of cyclohexanone oxime is only 95%.
  • the study found that due to the large molecular size of cyclododecanone and its physicochemical properties different from cyclohexanone, the use of commercial Ti-MWW molecular sieves for direct ammoximation cannot obtain a sufficiently high ketone conversion rate. and sufficiently high oxime selectivity.
  • Patent CN1860098 describes a co-ammoximation reaction, that is, a method for simultaneously performing ammoximation on ketones, especially cyclic ketones such as cyclododecanone and cyclohexanone.
  • the so-called ammoximation reaction can be understood as the process of preparing oximes from ketones or aldehydes using hydrogen peroxide and ammonia and using catalysts consisting essentially of silicon, titanium and oxygen, such as titanium silicalite.
  • the reaction system needs to be designed to mix two-component mixed ketones, and the product is a mixed oxime compound.
  • cyclohexanone oxime or cyclododecanone oxime contains traces of another component oxime, which will inevitably affect the subsequent rearrangement process and further affect the downstream nylon 6 and nylon 12 products. the quality of.
  • cyclohexanone oxime and cyclododecanone oxime are heat-sensitive raw materials, and the heat-sensitive by-products of cyclohexanone oxime are easily mixed into the cyclododecanone oxime rectification product.
  • the oximation process of macrocycloalkanone is divided into two processes: the oximation of hydroxylamine salt by Raschig liquid method and the oximation of green aminooxime.
  • both processes have obvious problems in the process of industrial scale-up.
  • the Lassi liquid oximation process contains four difficulties. 1
  • 1 The pH control of Lassi liquid is relatively fine, the operation flexibility is narrow, and the production chain control is unstable; 2
  • the hydroxylamine salt by-product produces ammonium sulfate, ammonium hydrochloride, etc., and a large number of three wastes produce serious damage to the environment; 3
  • 4 Hydroxylamine salt is a solid compound, and there is dust pollution in industrial production feeding, and the operating environment is harmful to health.
  • the macrocycloalkanone ammoximation process contains three difficulties. 1 The mixed system of two ketones realizes the ammoximation reaction, and the separation energy consumption is high; 2 The reaction system involves material separation, the macrocycloalkanone oximation product has a high boiling point, and the energy consumption of separation by rectification is high, so it is urgent to seek high efficiency and low energy. 3. The hydroxylamine intermediate is easily decomposed, the effective utilization is low, and the hydrogen peroxide feed ratio is high, resulting in a low effective utilization rate of hydrogen peroxide. A variety of factors jointly affect the industrialization process of macrocycloalkanone oximation process. Therefore, the development of a green and efficient process based on amidoximation has attracted much attention.
  • the present invention aims to propose a method for oximation of macrocycloalkanones to solve the above problems.
  • a method for ammoximation of macrocycloalkanone comprising the following steps:
  • step b the mixed solution obtained in step a is reacted in the oximation reactor to obtain a reaction solution;
  • step b The reaction solution obtained in step b is gradually lowered from the reaction temperature to 0-40° C., and cycloalkanone oxime is obtained by cooling and crystallization through a crystallizer.
  • the mass fraction of hydrogen peroxide in step a is 5%-80%, and the amount of hydrogen peroxide is 0.1-1.02 moles of macrocycloalkanone, preferably, the mass fraction of hydrogen peroxide is 27.5%-50%, hydrogen peroxide
  • the dosage is 0.9-1.0 of the molar amount of macrocycloalkanone.
  • the mass fraction of ammonia water used in step a is 10%-100%, and the amount of ammonia used is 1.0-10.0 of the molar amount of hydrogen peroxide.
  • the dosage is 1.0-3.0 of the molar amount of hydrogen peroxide.
  • the hydroxylamine stabilizer includes organic acid and mineral acid, and the organic acid is formic acid, acetic acid, propionic acid, n-butyric acid, n-valeric acid, oxalic acid, malonic acid, 1,4-butanedi acid, chloroacetic acid, dichloroacetic acid, 1,5-glutaric acid, 1,6-adipic acid, methanesulfonic acid, benzenesulfonic acid, p-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid and p-methylsulfonic acid
  • the mixture of one or more in benzenesulfonic acid, described mineral acid is the mixture of one or more in boric acid, pyrophosphoric acid, phosphoric acid and phosphorous acid, and described hydroxylamine stabilizer quality is macrocycloalkanone quality. 0.1%-50%, preferably, the mass of the hydroxylamine stabilizer is 5%-15% of the
  • the oximation catalyst in step a is TS-1, TS-2, Ti-Beta, Ti-ZSM-48, Ti-MCM-41, Ti-SSZ-42, Ti-MCM-48, Ti- A mixture of one or more of MSU, Ti-MWW and Ti-SBA-15, the mass of the oximation catalyst is 5%-50% of the mass of the macrocycloalkanone, preferably, the mass of the oximation catalyst is It is 10%-20% of the mass of macrocycloalkanone, and the oximation catalyst is TS-1, Ti-MWW or a mixture of the two.
  • the solvent is a tertiary alcohol solvent
  • the total carbon number is 4-8
  • the quality of the solvent is 50%-600% of the mass of the macrocycloalkanone.
  • the quality of the solvent is 150%-200% of the mass of the macrocycloalkanone
  • the solvent is a tertiary alcohol solvent with a total carbon number of 4 or 5.
  • the reaction temperature is 40-120°C, and the reaction residence time is 0.5-6h, preferably, the reaction temperature is 68-88°C, and the reaction residence time is 1.5-2.5h.
  • the oximation reactor is a 1-stage or less than or equal to 12-stage series device
  • the crystallization separator is a 1-stage or less than or equal to 12-stage series device, preferably step b
  • the oximation reactor in and the crystallization separator in step c are both 2-4 stage series devices.
  • step c the reaction solution is gradually lowered from the reaction temperature to 10-25°C.
  • the macrocycloalkanone oxime obtained in step c is cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cycloundecanone oxime, cyclododecanone oxime, cyclotridecone oxime, cyclotetradecone oxime Keto oxime, cyclopentadecanone oxime and cyclohexadecone ketoxime and derivatives thereof, further prepared from oxime corresponding to capryllactam, nonylactam, caprolactam, undecanolactam, laurolactam, tridecalactam , tetradecanolactam, pentadecalactam and hexadecanolactam and their derivatives, the content of macrocycloalkanone oxime is 99.9%.
  • the method for oximation of macrocycloalkanone of the present invention has the following advantages:
  • the method for oximation of macrocycloalkanone according to the present invention can realize the utilization rate of hydrogen peroxide of 98.3%-99.9%, the molar yield of macrocycloalkanone oxime corresponding to macrocycloalkanone is 99.2%-99.9%, and the cooling crystallization separation
  • the macrocycloalkanone oxime with a content of 99.9% is obtained, and after the mother liquor is distilled to remove water through a water removal tower, the solvent system can be recycled;
  • the method for oximation of macrocycloalkanones of the present invention uses a hydrogen peroxide concentration range of 5% to 80% to overcome the limitation of hydrogen peroxide concentration;
  • the method for oximation of macrocycloalkanones according to the present invention adopts a crystallization separation process at a temperature of 0 to 40° C., the cooling energy is coupled, the separation energy consumption is reduced, and the separation efficiency is improved;
  • the method for oximation of macrocycloalkanone according to the present invention adds stabilizer to inhibit the decomposition of hydroxylamine, and the utilization rate of hydrogen peroxide is 98.3%-99.9%;
  • the method for oximation of macrocycloalkanones of the present invention is suitable for macrocycloalkanones with carbon numbers of 8-16, and has strong universality;
  • the solvent in the method for oximation of macrocycloalkanone of the present invention can be directly used in the system after simply removing part of the water, the solvent reuse process is simple, and the energy consumption advantage is obvious;
  • Ammonia water or liquid ammonia in the method for oximation of macrocycloalkanone according to the present invention can realize oximation reaction, avoid the restriction of ammonia form, and reduce the cost of using ammonia.
  • Fig. 1 is the reaction principle schematic diagram described in the embodiment of the present invention.
  • Fig. 2 is the schematic diagram of the solubility curve of cyclodecanone and cyclodecane oxime described in the embodiment of the present invention
  • FIG. 3 is a schematic structural diagram of a crystallizer separator according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram of the crystal structure of cyclodecoxime under different cooling rates according to the embodiment of the present invention, wherein the cooling rate of a is 3 °C/min, the cooling rate of b is 0.5 °C/min, and the cooling rate of c is 10 °C /min.
  • test reagents used in the following examples are conventional biochemical reagents unless otherwise specified; the experimental methods are conventional methods unless otherwise specified.
  • the method for the ammoximation of macrocycloalkanone in the present invention is to put hydrogen peroxide, ammonia water, hydroxylamine stabilizer, oximation catalyst, solvent and macrocycloalkanone with a total carbon number of 8-16 into the oximation reactor and mix. , heated to an appropriate temperature to carry out the reaction, and then the reaction temperature was gradually lowered to 0-40 ° C, and the cycloalkanone oxime was obtained by cooling and crystallization through a crystallizer.
  • the hydroxylamine stabilizer is a weak acid with an ionization constant of 1.0*10 -6 ⁇ Ka ⁇ 1.0*10 -3 at 25°C
  • the solvent is a tertiary alcohol solvent
  • the total carbon number is 4-8.
  • cyclodecanone to prepare cyclodecane oxime as an example, as shown in Figure 2, the solvent is tert-butanol, the solubility of cyclodecanone at 10 °C is 37.5g/100g, the solubility of cyclodecane oxime is only 0.3g/100g, and the solubility of cyclodecanone is only 0.3g/100g. It is 125 times more soluble than oxime, and the huge solubility difference provides a guarantee for crystallization separation.
  • the step-by-step cooling method is adopted for crystallization.
  • the effects of different cooling rates on the crystallization are shown in Table 1 and Figure 4.
  • the cooling rate is relatively fast, the crystals grow slender and the separation effect is poor.
  • the cooling speed is relatively slow, the crystal grows in bulk, and the separation effect is good.
  • 1 or less than or equal to 12 series series devices are continuously cooled to improve production efficiency.
  • the crystallization separator used in the present invention is a 1-stage or less than or equal to 12-stage series device, taking 3-stage series as an example, as shown in FIG. Most of the cooling liquid discharged from the device enters the next stage crystallization separator or is discharged, and a small part is returned to the crystallization separator for auxiliary cooling, and the temperature of the crystallization separator in the upper stage is higher than that in the next stage. The temperature of the crystallization separator, so that the saturated solution discharged from the crystallization separator of the previous stage forms a supersaturated solution in the crystallization separator of the next stage, which is helpful for the crystallization of the product.
  • the flow rate of cyclododecanone is 0.364Kg/h
  • the flow rate of tert-butanol is 0.23Kg/h
  • the flow rate of n-butyric acid is 0.02Kg/h
  • the flow rate of 10% ammonia water is 0.34Kg/h
  • the flow rate of 30% hydrogen peroxide is 0.226Kg/h .
  • the three-stage reactor is connected in series, the volume of a single reactor is 1L, the mass of the filled catalyst TS-1 in each stage of the reactor is 0.012Kg, the control liquid level of each stage of the reactor is 0.5h, and the residence time of each stage of the reactor is 0.5h, and the control reaction temperature is 81°C.
  • the mother liquor of the third-stage reactor enters the 3-stage crystallizer series device, the first-stage crystallizer is cooled to 40 °C, the first-stage crystallizer solid-liquid separation mother liquor enters the second-stage crystallizer and the temperature is lowered to 20 °C, and the second-stage crystallizer solid-liquid
  • the separated mother liquor enters the third-stage crystallizer to cool down to 0°C.
  • the cyclododecanone oxime 1/2/3 stage crystallizer separation product distribution is 93.3%, 5.3%, 1.4%.
  • the mother liquor of the third stage crystallizer is rotary evaporated to remove moisture, and the mother liquor is recycled.
  • Example 1 The difference from Example 1 is that the raw material used in Comparative Example 1 was cyclohexanone, and no formic acid was added. Other conditions were the same as those in Example 1. The conversion rate of cyclohexanone was 95.0%, the selectivity was 98.6%, and hydrogen peroxide was used. The effective utilization rate is 93.67%.
  • Example 1 The difference with Example 1 is that no formic acid was added in Comparative Example 2, other conditions were the same as Example 3, the conversion rate of obtaining cyclooctanone was 10.3%, the selectivity was 95.1%, and the effective utilization rate of hydrogen peroxide was 9.80%.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé d'ammoximation de la macrocycloalcanone, comprenant les étapes suivantes consistant à : ajouter du peroxyde d'hydrogène, de l'eau ammoniaquée, un stabilisateur d'hydroxylamine, un catalyseur d'oximation, un solvant, et une macrocycloalcanone dans un réacteur d'oximation pour une réaction afin d'obtenir une solution de réaction, refroidir la solution de réaction d'une température de réaction à 0-40 °C progressivement, et effectuer une cristallisation par refroidissement au moyen d'un séparateur de cristallisation pour obtenir une oxime de cycloalcanone. Le procédé d'oximation de la macrocycloalcanone fourni par la présente invention permet d'obtenir un taux d'utilisation de la solution de peroxyde d'hydrogène de 98,3 % à 99,9 %, un rendement molaire de l'oxime de macrocycloalcanone correspondant à la macrocycloalcanone de 99,2 % à 99,9 %, de l'oxime de macrocycloalcanone ayant une teneur de 99,9 % obtenue au moyen d'une séparation de cristallisation par refroidissement, et une solution mère distillée par une colonne d'élimination d'eau pour obtenir une utilisation cyclique du système de solvant.
PCT/CN2021/114318 2020-11-30 2021-08-24 Procédé d'ammoximation de la macrocycloalcanone WO2022110930A1 (fr)

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