CN113480448B - Method for preparing 6-aminocapronitrile - Google Patents
Method for preparing 6-aminocapronitrile Download PDFInfo
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- CN113480448B CN113480448B CN202110766644.1A CN202110766644A CN113480448B CN 113480448 B CN113480448 B CN 113480448B CN 202110766644 A CN202110766644 A CN 202110766644A CN 113480448 B CN113480448 B CN 113480448B
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Abstract
The invention provides a method for preparing 6-aminocapronitrile, which comprises the following steps: (1) Respectively preheating caprolactam and ammonia gas, and introducing the caprolactam and the ammonia gas into a micro-channel reactor I together for reaction to obtain 6-aminocaproamide; (2) Carrying out gas-liquid separation on the material obtained after the reaction in the step (1) to obtain a liquid-phase material 6-aminocaproamide; (3) Preheating the 6-aminocaproamide obtained by separation in the step (2), introducing the preheated 6-aminocaproamide into a micro-channel reactor II, and simultaneously introducing a dehydrating agent for dehydration reaction to obtain the 6-aminocapronitrile. The method effectively controls the polymerization of ammonolysis products, reduces the generation of byproducts, uses the dehydrating agent to carry out dehydration reaction under the condition of no catalyst, and effectively avoids the problems of catalyst coking, short service life of the catalyst and the like in the catalytic dehydration process.
Description
Technical Field
The invention belongs to the technical field of hexamethylenediamine synthesis, and particularly relates to a method for preparing 6-aminocapronitrile serving as a key intermediate of hexamethylenediamine by a two-step method.
Background
1, 6-hexamethylene diamine is an important intermediate of high-performance materials such as nylon 66, nylon 610 and the like, is also used in the production of polyurethane such as 1, 6-Hexamethylene Diisocyanate (HDI), and can be used as a curing agent of urea-formaldehyde resin and epoxy resin.
According to different raw materials, the production method of hexamethylenediamine mainly comprises four steps: the butadiene process, the acrylonitrile process, the adipic acid process and the caprolactam process, respectively.
In the butadiene method, complex compounds of transition metals such as Rh, ni, ru and the like are generally adopted as catalysts, two molecules of hydrocyanic acid are introduced into butadiene, adiponitrile is prepared by addition reaction, and 1, 6-hexamethylenediamine is prepared by hydrogenation; the method has the advantages that the cost of raw materials is low, equipment is easy to automatically control, and the product quality is good; the method has the defects that the use of the highly toxic hydrocyanic acid has extremely high requirements on production equipment, operation and management, great occupational hazard, great difficulty in catalyst preparation technology and high construction investment.
The method for synthesizing adiponitrile by electrolytic dimerization of acrylonitrile uses propylene as a raw material, firstly uses oxygen, ammonia and a catalyst to convert the propylene into acrylonitrile, then uses the acrylonitrile to be electrolytically reduced into adiponitrile, and then obtains 1, 6-hexamethylenediamine through hydrogenation reduction and refining; the method has the advantages of simple process flow and high conversion rate; the method has the defects of more nodes of the electrolysis process technology, high control difficulty and high safety risk.
The adipic acid is subjected to ammoniation and dehydration to prepare adiponitrile in a molten state by an adipic acid method, and then 1, 6-hexamethylenediamine is obtained through hydrogenation reduction and refining; the method has the advantages that the technical route is relatively mature, the raw material adipic acid is excessive in capacity, and the manufacturing cost of adiponitrile gradually has certain competitiveness along with the reduction of the manufacturing cost of adipic acid; the defects are high energy consumption, easy coking and corrosion of the reactor, low product yield and poor quality.
The caprolactam method is from the 60 th century of 20, and the eastern company of japan takes waste nylon as a raw material to obtain caprolactam after depolymerization, then reacts with ammonia gas under the action of a catalyst to obtain 6-aminocapronitrile, and further hydrogenation reduction and refining are carried out to obtain 1, 6-hexamethylenediamine. The process has high caprolactam price, high product manufacturing cost, and can not be popularized on a large scale, and the eastern device in japan stops production in 1989.
However, with the improvement of the caprolactam preparation process, especially with the popularization and application of the new process, the total capacity of caprolactam at home and abroad in 2019 is 771 ten thousand tons/year, wherein the domestic capacity is 401 ten thousand tons/year, the foreign capacity is 370 ten thousand tons/year, the Chinese capacity ratio is up to 52%, and the domestic capacity in 2021 can reach 559 ten thousand tons; expert predicts that the caprolactam productivity will reach 1000 ten thousand tons in 2025; with the reduction of caprolactam manufacturing costs, the process of preparing hexamethylenediamine from caprolactam is also more competitive.
The Chinese patent application with application number 201710943063.4 discloses a method and a device for preparing 6-aminocapronitrile by adopting a one-step liquid-phase caprolactam liquid-phase method, wherein the process is characterized in that caprolactam and ammonia are subjected to ammonolysis and dehydration in a reaction kettle under the condition of taking phosphoric acid or phosphate as a catalyst to prepare the 6-aminocapronitrile, but the caprolactam conversion rate in the process is only 50-60%, the catalyst is difficult to recover, and the manufacturing cost is high.
CN107602416a discloses a method for preparing 6-aminocapronitrile by a one-step method of caprolactam gas phase method, the process is that caprolactam is heated and gasified and then mixed with hot ammonia gas, and the mixture is passed through a fixed bed reactor to make contact with catalyst to make ammonification dehydration reaction so as to prepare 6-aminocapronitrile, and the conversion rate of the reaction is raised to 96%. However, caprolactam is easy to open loop and self-polymerize in the process of vaporization and reaction in the presence of trace water, so that the reaction selectivity is reduced, the generated polymer is adhered to the surface of the catalyst, and cokes under the high-temperature condition, so that the stable operation of the device and the service life of the catalyst are influenced.
CN111662210a discloses a method and apparatus for preparing 6-aminocapronitrile by two steps, firstly, hydrolyzing caprolactam, then ammoniating, first dehydrating to obtain 6-aminocaproamide, and secondly, catalyzing, ammoniating and dehydrating 6-aminocaproamide to obtain 6-aminocapronitrile.
CN111978207a discloses a method for synthesizing a key intermediate of hexamethylenediamine. Firstly preheating caprolactam and ammonia water, then introducing the preheated caprolactam and ammonia water into a microchannel reactor, separating to obtain 6-aminocaproamide, gasifying the 6-aminocaproamide, and carrying out catalytic dehydration with ammonia gas to obtain 6-aminocapronitrile.
CN111662210a and CN111978207a are essentially two-step processes, where 6-aminocaproamide is first produced, followed by further catalytic dehydration to give 6-aminocapronitrile. However, in the first step, caprolactam is firstly hydrolyzed and ring-opened with water to obtain 6-aminocaproic acid, and then ammoniated and dehydrated to obtain 6-aminocaproamide. After the reaction is finished, more energy is required to be consumed to remove free water, the polymerization degree of caprolactam is increased due to the introduction of water, and then the polymer is easy to coke at high temperature through subsequent catalytic ammonification and dehydration, so that the total reaction yield is unstable, and the product quality is also affected.
Disclosure of Invention
The invention mainly aims to provide a continuous preparation method of hexamethylenediamine key intermediate 6-aminocapronitrile, which aims to solve the problems that in the prior art, the catalyst for preparing 6-aminocapronitrile is easy to coke and deactivate and the running stability of a device is affected, and also solves the problems that in the original two-step method, the energy consumption is increased, the polymer is increased and the catalyst is coked in the catalytic ammonification dehydration.
In order to achieve the above object, the present invention provides a method for preparing hexamethylenediamine key intermediate 6-aminocapronitrile using a microchannel reactor, comprising: (1) After respectively preheating caprolactam and ammonia gas, introducing the caprolactam and the ammonia gas into a micro-channel reactor I together for reaction to obtain 6-aminocaproamide, wherein the reaction equation is as follows:
(2) Carrying out gas-liquid separation on the material obtained after the reaction in the step (1) to obtain a liquid-phase material 6-aminocaproamide;
(3) Preheating the 6-aminocaproamide obtained by separation in the step (2), introducing the preheated 6-aminocaproamide into a micro-channel reactor II, and simultaneously introducing a dehydrating agent for dehydration reaction to obtain 6-aminocapronitrile, wherein the reaction equation is as follows:
further, in step (1), the molar ratio of caprolactam to ammonia is preferably 1: (1 to 100), more preferably 1: (1-30); the preheating temperature of caprolactam is preferably 200-450 ℃, more preferably 250-350 ℃; the preheating temperature of the ammonia gas is preferably 150-450 ℃, more preferably 200-350 ℃; when the reaction is carried out in the micro-channel reactor I, the reaction temperature is preferably 300-650 ℃, more preferably 350-450 ℃; the reaction pressure is preferably 0.1MPa to 10MPa, more preferably 0.2 MPa to 5MPa; the reaction time is preferably 0.1 to 10 minutes, more preferably 0.2 to 2 minutes.
Further, in the step (2), the temperature at which the material is separated is preferably 100 to 300 ℃.
Further, in the step (3), the preheating temperature of the 6-aminocaproamide is controlled to be preferably 200 to 500 ℃, more preferably 300 to 400 ℃.
Further, in the step (3), the dehydrating agent is preferably one or more selected from phosgene, triphosgene, thionyl chloride, phosphorus pentoxide, p-toluenesulfonyl chloride, dicyclohexylcarbodiimide (DCC), phosphorus o-phenylene trichloride, titanium tetrachloride-tertiary amine, triphenylphosphine-carbon tetrachloride-triethylamine, trichloroacetyl chloride-triethylamine, trifluoromethanesulfonic anhydride-triethylamine, dibutyltin oxide, etc., preferably one or more selected from phosgene, triphosgene, thionyl chloride, etc.
Further, in the step (3), preferably, the dehydrating agent is subjected to a dehydration reaction after being preheated, and the preheating temperature of the dehydrating agent is preferably 150 to 400 ℃, more preferably 200 to 300 ℃; the preferred molar ratio of 6-aminocaproamide to dehydrating agent is 1: (1 to 20), more preferably 1: (1-12); the reaction temperature is preferably 300 to 650 ℃, more preferably 350 to 450 ℃; the reaction pressure is preferably 0.1MPa to 10MPa, more preferably 0.1MPa to 5MPa; the reaction time is preferably 0.1 to 10 minutes, more preferably 0.5 to 5 minutes.
Further, in the step (2), preferably, the material obtained after the reaction in the step (1) is subjected to gas-liquid separation, and the material remaining after the separation of 6-aminocaproamide is sent to the step (1) for continuous reaction.
According to the invention, two steps of ammonolysis ring opening and dehydration are continuously carried out in a two-stage microchannel reactor, and in the first step, the ammonolysis ring opening reaction is carried out under anhydrous conditions, so that the hydrolytic polymerization of caprolactam is avoided, and a 6-aminocaproamide crude product is obtained; after the crude product is conventionally separated, a dehydrating agent is added, and under the condition of no catalyst, 6-aminocaproamide and the dehydrating agent are continuously dehydrated in a microchannel reactor to obtain the target product 6-aminocapronitrile.
The microchannel reactor herein may employ any microchannel reactor suitable in the art. The microchannel reactors I and II may have the same or different structures. For example, the microchannel reactor may be a microchannel reactor of the G1 module of Corning corporation of America, the structure of which is shown in FIGS. 1 and 2. As shown in fig. 1, the microchannel reactor has reactant inlets and product outlets and heat exchange medium inlets and outlets, and a reaction layer intermediate the two heat transfer layers. A schematic of the microchannel mixing structural unit in the reaction layer is shown in fig. 2.
The method effectively controls the polymerization of ammonolysis products, reduces the generation of byproducts, uses the dehydrating agent to carry out dehydration reaction under the condition of no catalyst, and effectively avoids the problems of catalyst coking, short service life of the catalyst and the like in the catalytic dehydration process. As caprolactam is subjected to ring opening ammonolysis to form chain molecules, 6-aminocaproamide is obtained by fully ammonifying the caprolactam as much as possible, the conversion rate and selectivity of the caprolactam are improved, and the requirement on the contact time of ammonia, caprolactam and products is reduced. The whole process is continuously carried out, the production cost is low, and the method is suitable for realizing industrial production.
Drawings
FIG. 1 is a block diagram of a microchannel reactor (schematic diagram of the module structure of G1 from Corning Co., USA).
FIG. 2 is a schematic diagram of a microchannel mixing building block.
Detailed Description
Hereinafter, the present invention will be described in detail by way of examples. However, the examples provided herein are for illustrative purposes only and are not intended to limit the present invention.
The experimental methods used in the examples below are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Drug information:
caprolactam, CAS number: 105-60-2, industrial priority, asahi Kabushiki Kaisha, cangzhou chemical Co., ltd;
liquid ammonia, CAS number: 7664-41-7, industrial grade, hebei Xuanyang coking Co., ltd;
triphosgene, CAS number: 32315-10-9, reagent AR grade, beijing Walker Biotech Co., ltd;
thionyl chloride, CAS number: 7719-09-7, reagent AR grade, national drug group chemical reagent limited;
phosgene, CAS number: 75-44-5, industrial grade, large group, inc;
p-toluenesulfonyl chloride, CAS number: 98-59-9, reagent AR grade, alpha reagent.
Instrument information:
a temperature control metering pump, CP050T, the temperature control range is 30-140 ℃, and Tianjin air-curing aster science and technology development Co., ltd;
a microchannel reactor, corning company G1 microchannel reactor module in the united states;
gas chromatograph: agilent 7890B, chromatographic column: HP-5, 30 m.320.25 um.
Caprolactam conversion and 6-aminocaproamide selectivity were calculated as follows:
total mass M of caprolactam metered in Inlet 1 Mole number R and total mass M of discharged sample Go out 1 (comprising collecting materials by a sampling port sample and a condensation recovery system), and testing the mass percent of 6-aminocaproamide and caprolactam of a discharged sample by a GC external standard method, thereby calculating the mole number G of the 6-aminocaproamide and the mole number H of the caprolactam of the discharged sample.
The 6-aminocaproamide conversion and 6-aminocapronitrile selectivity were calculated as follows:
total mass M of 6-aminocaproamide metered in Inlet 2 Number of moles N and total mass M of discharged sample Go out 2 (comprising sampling port samples and collecting materials by a condensation recovery system), testing the mass percent content of 6-aminocapronitrile and 6-aminocaproamide of a discharged sample by a GC external standard method, and calculating the mole number D of the 6-aminocapronitrile and the mole number E of the 6-aminocaproamide of the discharged sample.
Example 1
The method for synthesizing the hexamethylenediamine key intermediate 6-aminocapronitrile comprises the following steps:
(1) Respectively conveying raw caprolactam into different preheaters through a temperature control metering pump and ammonia gas to preheat, wherein the preheating temperature of the caprolactam is 280 ℃, the preheating temperature of the ammonia gas is 350 ℃, introducing the preheated caprolactam and the ammonia gas into a microchannel reactor I according to a molar ratio of 1:30, and reacting at 450 ℃ under 5MPa, wherein the residence time of the microchannel reactor I is 15s;
(2) Delivering the material obtained after the reaction in the step (1) into a gas-liquid separator, performing gas-liquid separation at 200 ℃, delivering the gas-phase material ammonia obtained by separation into the step (1) for continuous reaction, and separating to obtain a liquid-phase material of 6-aminocaproamide;
(3) Pumping the 6-aminocaproamide separated in the step (2) into a preheater by a temperature control metering pump, and directly introducing the preheated 6-aminocaproamide into a microchannel reactor II at the preheating temperature of 300 ℃; the triphosgene dehydrating agent enters a micro-channel reactor II together with 6-aminocaproamide according to a molar ratio of 6:1, reacts at 350 ℃ and 0.1MPa, stays for 30 seconds in the micro-channel reactor II, and is separated to obtain the 6-aminocapronitrile after the reaction is finished.
Analysis of the materials and products of the above examples showed that: the caprolactam conversion is 99.2% and the 6-aminocaproamide selectivity is 98.9%; the conversion of 6-aminocaproamide was 96.3% and the selectivity to 6-aminocapronitrile was 98.8%.
Example 2
The method for synthesizing the hexamethylenediamine key intermediate 6-aminocapronitrile comprises the following steps:
(1) Respectively conveying raw caprolactam into different preheaters through a temperature control metering pump and ammonia gas to preheat, wherein the preheating temperature of the caprolactam is 300 ℃, the preheating temperature of the ammonia gas is 350 ℃, introducing the preheated caprolactam and the ammonia gas into a micro-channel reactor I according to a molar ratio of 1:20, and reacting at 350 ℃ under 1MPa, wherein the residence time of the micro-channel reactor I is 60s;
(2) Delivering the material obtained after the reaction in the step (1) into a gas-liquid separator, performing gas-liquid separation at 250 ℃, delivering the gas-phase material ammonia obtained by separation into the step (1) for continuous reaction, and separating to obtain a liquid-phase material of 6-aminocaproamide;
(3) Pumping the 6-aminocaproamide separated in the step (2) into a preheater by a temperature control metering pump, and directly introducing the preheated 6-aminocaproamide into a microchannel reactor II at the preheating temperature of 400 ℃; the dehydration agent thionyl chloride is preheated to 200 ℃, enters a micro-channel reactor II together with 6-aminocaproamide according to a molar ratio of 12:1, reacts at 450 ℃ and 5MPa, stays for 5min in the micro-channel reactor II, and is separated to obtain 6-aminocapronitrile after the reaction is finished.
Analysis of the materials and products of the above examples showed that: caprolactam conversion was 97.3% and 6-aminocaproamide selectivity was 95.9%; the conversion of 6-aminocaproamide was 94.3% and the selectivity to 6-aminocapronitrile was 97.8%.
Example 3
The method for synthesizing the hexamethylenediamine key intermediate 6-aminocapronitrile comprises the following steps:
(1) Respectively conveying raw caprolactam into different preheaters through a temperature control metering pump and ammonia gas to preheat, wherein the preheating temperature of the caprolactam is 250 ℃, the preheating temperature of the ammonia gas is 200 ℃, introducing the preheated caprolactam and the ammonia gas into a micro-channel reactor I according to a molar ratio of 1:10, and reacting at 400 ℃ under 5MPa, wherein the residence time of the micro-channel reactor I is 120s;
(2) Delivering the material obtained after the reaction in the step (1) into a gas-liquid separator, performing gas-liquid separation at 200 ℃, delivering the gas-phase material ammonia obtained by separation into the step (1) for continuous reaction, and separating to obtain a liquid-phase material of 6-aminocaproamide;
(3) Pumping the 6-aminocaproamide separated in the step (2) into a preheater by a temperature control metering pump, and directly introducing the preheated 6-aminocaproamide into a microchannel reactor II, wherein the preheating temperature is 350 ℃; the phosgene pre-heating temperature of the dehydrating agent is 200 ℃, the dehydrating agent and 6-aminocaproamide are fed into a micro-channel reactor II together according to the mol ratio of 10:1, the reaction is carried out at 400 ℃ and 4MPa, the residence time of the micro-channel reactor II is 4min, and the 6-aminocapronitrile is obtained after the reaction is finished.
Analysis of the materials and products of the above examples showed that: the caprolactam conversion was 96.9% and the 6-aminocaproamide selectivity was 93.8%; the conversion of 6-aminocaproamide was 98.5% and the selectivity to 6-aminocapronitrile was 98.3%.
Example 4
The method for synthesizing the hexamethylenediamine key intermediate 6-aminocapronitrile comprises the following steps:
(1) Respectively conveying raw caprolactam into different preheaters through a temperature control metering pump and ammonia gas to preheat, wherein the preheating temperature of the caprolactam is 300 ℃, the preheating temperature of the ammonia gas is 350 ℃, introducing the preheated caprolactam and the ammonia gas into a micro-channel reactor I according to a molar ratio of 1:28, and reacting at 450 ℃ under 3MPa, wherein the residence time of the micro-channel reactor I is 80s;
(2) Delivering the material obtained after the reaction in the step (1) into a gas-liquid separator, performing gas-liquid separation at 250 ℃, delivering the gas-phase material ammonia obtained by separation into the step (1) for continuous reaction, and separating to obtain a liquid-phase material of 6-aminocaproamide;
(3) Pumping the 6-aminocaproamide separated in the step (2) into a preheater by a temperature control metering pump, and directly introducing the preheated 6-aminocaproamide into a microchannel reactor II at the preheating temperature of 400 ℃; the dehydrating agent is preheated to 300 ℃ for tosyl chloride, and the dehydrating agent and 6-aminocaproamide are mixed according to the mol ratio of 6:1 enters a micro-channel reactor II to react at 420 ℃ and 3MPa, the residence time of the micro-channel reactor II is 3min, and the 6-aminocapronitrile is obtained after the reaction is finished.
Analysis of the materials and products of the above examples showed that: caprolactam conversion was 97.9% and 6-aminocaproamide selectivity was 98.5%; the conversion of 6-aminocaproamide was 96.7% and the selectivity to 6-aminocapronitrile was 97.6%.
Claims (9)
1. A method of making 6-aminocapronitrile using a microchannel reactor comprising:
(1) After respectively preheating caprolactam and ammonia gas, introducing the caprolactam and the ammonia gas into a micro-channel reactor I together for reaction to obtain 6-aminocaproamide, wherein the reaction equation is as follows:
wherein, the mole ratio of caprolactam to ammonia is 1: (1-30);
the preheating temperature of caprolactam is 250-350 ℃;
the preheating temperature of ammonia gas is 150-450 ℃;
the reaction temperature is 300-650 ℃;
the reaction pressure is 0.1MPa to 10MPa;
the reaction time is 0.1 min-10 min;
(2) Carrying out gas-liquid separation on the material obtained after the reaction in the step (1) to obtain a liquid-phase material 6-aminocaproamide;
(3) Preheating the 6-aminocaproamide obtained by separation in the step (2), introducing the preheated 6-aminocaproamide into a micro-channel reactor II, and simultaneously introducing a dehydrating agent for dehydration reaction to obtain 6-aminocapronitrile, wherein the reaction equation is as follows:
wherein the preheating temperature of the 6-aminocaproamide is controlled to be 200-500 ℃;
the dehydrating agent is one or more selected from phosgene, triphosgene, thionyl chloride, phosphorus pentoxide and p-toluenesulfonyl chloride,
the dehydrating agent is dehydrated after being preheated, the preheating temperature of the dehydrating agent is 150-400 ℃,
the molar ratio of 6-aminocaproamide to dehydrating agent is 1: (1-20),
the reaction temperature is 300-650 ℃,
the reaction pressure is 0.1 MPa-10 MPa,
the reaction time is 0.1 min-10 min.
2. The method according to claim 1,
wherein in step (1), the molar ratio of caprolactam to ammonia is 1: (1-30); and/or
Wherein, in the step (1), the preheating temperature of caprolactam is 250-350 ℃; and/or
Wherein, in the step (1), the preheating temperature of ammonia gas is 200-350 ℃; and/or
Wherein in the step (1), when the reaction is carried out in the micro-channel reactor I, the reaction temperature is 350-450 ℃; and/or
Wherein in the step (1), when the reaction is carried out in the micro-channel reactor I, the reaction pressure is 0.2-5 MPa; and/or
Wherein, when the reaction is carried out in the micro-channel reactor I, the reaction time is 0.2-2 min.
3. A process according to claim 1 or 2, wherein in step (2) the material is separated at a temperature of 100 to 300 ℃.
4. The method according to claim 1 or 2, wherein in the step (3), the preheating temperature of the 6-aminocaproamide is controlled to 300 to 400 ℃.
5. The method according to claim 1 or 2, wherein in the step (3), the dehydrating agent is one or more selected from phosgene, triphosgene, thionyl chloride.
6. The method according to claim 1 or 2, wherein in the step (3), the preheating temperature of the dehydrating agent is 200 to 300 ℃.
7. The process according to claim 1 or 2, wherein in step (3), the molar ratio of 6-aminocaproamide to dehydrating agent is 1: (1-12).
8. The method according to claim 1 or 2, wherein in the step (3), the reaction temperature is 350 to 450 ℃; and/or the reaction pressure is 0.1 MPa-5 MPa; and/or the reaction time is 0.5 min-5 min.
9. The method according to claim 1 or 2, wherein in the step (2), the material obtained after the reaction in the step (1) is subjected to gas-liquid separation, and the residue obtained after the separation of 6-aminocaproamide is sent to the step (1) for continuous reaction.
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