A system and method for preparing hexamethylenediamine from butadiene

Abstract

The invention discloses a system device and method for preparing hexamethylenediamine from butadiene. The system device comprises a catalyst storage tank, a catalyst solution delivery pump, a 1,3-butadiene steel cylinder, a synthesis gas steel cylinder, a hydroformylation supergravity reactor, a first gas-liquid separation tank, a first heat exchanger, a second gas-liquid separation tank, a second heat exchanger, a third gas-liquid separation tank, a crude adipaldehyde heater, a first pressure reducing valve, an adipaldehyde flash tower, an adipaldehyde flash tower condenser, an adipaldehyde buffer tank, an adipaldehyde delivery pump, an ammonia steel cylinder, a hydrogen steel cylinder, a reduction amination supergravity reactor, an alcohol solvent storage tank, an alcohol solvent delivery pump, a catalyst filter, and the like. Hexamethylenediamine can be prepared by using the system device of the invention, highly toxic raw materials can be avoided, and the characteristics of mass transfer and mixing of the supergravity reactor can be enhanced, so that the selectivity and yield of the target product obtained by the reaction are improved, and the catalyst and solvent are recycled, so as to reduce the production cost and conform to the concept of green development.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical industry, and in particular relates to a system device and method for preparing hexamethylenediamine from butadiene. Background Art

[0002] Hexamethylenediamine is one of the three major nylon raw materials. Nylon 66 salt solution is generated by the condensation reaction of hexamethylenediamine and adipic acid, and then nylon 66 can be obtained through concentration and polycondensation. Polyamide products represented by nylon 66 are the engineering plastic products with the largest output and market demand in the world, and are widely used in industries such as automobiles, electronics, machinery, and electrical appliances.

[0003] The process routes for synthesizing hexamethylenediamine in industry are mainly divided into two categories. One is to synthesize adiponitrile from raw materials such as acrylonitrile and adipic acid, and then indirectly synthesize hexamethylenediamine from adiponitrile; the other is to directly synthesize hexamethylenediamine from raw materials such as hexamethylenediol and butadiene through conversion, skipping adiponitrile. In the above route, butadiene is hydroformylated to synthesize adipaldehyde, and then adipaldehyde is further aminated and hydrogenated to obtain hexamethylenediamine. The route avoids highly toxic raw materials such as hydrocyanic acid gas, sodium cyanide, potassium cyanide, etc., and the gas raw materials required for the reaction are cheap and easy to obtain. The yield and conversion rate of the amination hydrogenation stage in the process route are also high. It is a potential new industrial method. The reason for limiting the final hexamethylenediamine yield is the low yield of the hydroformylation reaction of conjugated olefins such as butadiene. Summary of the invention

[0004] The first technical problem to be solved by the present invention is to provide a system device for preparing hexamethylenediamine from butadiene.

[0005] The second technical problem to be solved by the present invention is to provide a method for preparing hexamethylenediamine from butadiene using the above-mentioned device.

[0006] In order to solve the above-mentioned first technical problem, the invention adopts the following technical solution:

[0007] A system device for preparing hexamethylenediamine from butadiene, comprising:

[0008] Catalyst storage tank, catalyst solution delivery pump, 1,3-butadiene steel cylinder, synthesis gas steel cylinder, hydroformylation supergravity reactor, first gas-liquid separation tank, first heat exchanger, second gas-liquid separation tank, second heat exchanger, third gas-liquid separation tank, crude adipaldehyde heater, first pressure reducing valve, adipaldehyde flash tower, adipaldehyde flash tower condenser, adipaldehyde buffer tank, adipaldehyde delivery pump, ammonia steel cylinder, hydrogen steel cylinder, reduction amination supergravity reactor, alcohol solvent storage tank, alcohol solvent delivery pump, catalyst filter, hexamethylenediamine cooler, dehydration tower, second pressure reducing valve, solvent flash tower, solvent flash tower condenser, cooling crystallizer and hexamethylenediamine product storage tank;

[0009] The catalyst storage tank, catalyst solution delivery pump, hydroformylation high gravity reactor, first gas-liquid separation tank, crude adipaldehyde heater, first pressure reducing valve, adipaldehyde flash tower, adipaldehyde flash tower condenser, adipaldehyde buffer tank, adipaldehyde delivery pump, reduction amination high gravity reactor, catalyst filter, hexamethylenediamine cooler, dehydration tower, second pressure reducing valve, solvent flash tower, cooling crystallizer and hexamethylenediamine product storage tank are sequentially connected through pipelines;

[0010] The 1,3-butadiene steel cylinder and the synthesis gas steel cylinder are respectively connected to the hydroformylation high-gravity reactor through pipelines;

[0011] The top of the first gas-liquid separation tank is connected to the inlet of the first heat exchanger through a pipeline, the outlet of the first heat exchanger is connected to the second gas-liquid separation tank through a pipeline, the bottom of the second gas-liquid separation tank is connected to the hydroformylation high-gravity reactor through a pipeline, and the top of the second gas-liquid separation tank is connected to the inlet of the second heat exchanger through a pipeline; the outlet of the second heat exchanger is connected to the third gas-liquid separation tank through a pipeline, and the bottom of the third gas-liquid separation tank is connected to the hydroformylation high-gravity reactor through a pipeline;

[0012] The ammonia gas cylinder and the hydrogen gas cylinder are respectively connected to the reduction ammonia high-gravity reactor through pipelines;

[0013] The top of the solvent flash tower is connected to the solvent flash tower condenser through a pipeline, the solvent flash tower condenser is connected to the alcohol solvent storage tank through a pipeline, the alcohol solvent storage tank is connected to the alcohol solvent delivery pump through a pipeline, and the alcohol solvent delivery pump is connected to the reduction amination supergravity reactor through a pipeline.

[0014] In order to solve the above second technical problem, the invention adopts the following technical solution:

[0015] A method for preparing hexamethylenediamine from butadiene using the above device comprises the following steps:

[0016] 1) Hydroformylation Section

[0017] 1.1) transporting the catalyst and solvent adipaldehyde stored in the catalyst raw material tank, as well as the raw material synthesis gas and 1,3-butadiene to the hydroformylation high-gravity reactor for hydroformylation reaction, and the hydroformylation reaction obtains a crude adipaldehyde solution A;

[0018] 1.2) The crude adipaldehyde solution A after the hydroformylation reaction is completed is sequentially transported to the first gas-liquid separation tank, the second gas-liquid separation tank and the third gas-liquid separation tank through pipelines, and the crude adipaldehyde solution B separated by the first gas-liquid separation tank is sent to the adipaldehyde flash tower for further refining by step-by-step gas-liquid separation and step-by-step cooling by the first heat exchanger and the second heat exchanger, and a small portion of the crude adipaldehyde solution C containing the catalyst separated by the first gas-liquid separation tank, the second gas-liquid separation tank and the third gas-liquid separation tank is transported to the hydroformylation high gravity reactor for continued catalytic reaction, and the mixed gas discharged from the top of the third gas-liquid separation tank is treated as tail gas;

[0019] 1.3) the crude adipaldehyde solution B separated by the first gas-liquid separation tank is heated by a crude adipaldehyde heater, then decompressed by a first pressure reducing valve, and enters an adipaldehyde flash tower for flash evaporation, adipaldehyde is evaporated at the top of the tower, cooled by an adipaldehyde flash tower condenser as an adipaldehyde solution and transported to an adipaldehyde buffer tank, and a part of the crude adipaldehyde solution D containing the catalyst flowing out of the bottom of the tower kettle of the adipaldehyde flash tower is transported to a catalyst raw material tank for recycling, and a part is discharged as waste liquid;

[0020] 2) Reduction ammonia chemical section

[0021] 2.1) transporting the adipaldehyde stored in the adipaldehyde buffer tank, the alcohol solvent and the Raney nickel catalyst stored in the alcohol solvent storage tank, the ammonia stored in the ammonia cylinder, and the hydrogen stored in the hydrogen cylinder to the reduction amination high gravity reactor via pipelines to undergo reduction amination reaction;

[0022] 2.2) After the reduction amination reaction, the crude hexamethylenediamine solution A is filtered through a catalyst filter and then cooled through a hexamethylenediamine cooler, and then transported to a dehydration tower, and subjected to water absorption treatment by a molecular sieve filled in the dehydration tower to obtain a crude hexamethylenediamine solution B;

[0023] 2.3) The crude hexamethylenediamine solution B after dehydration treatment is depressurized by a second pressure reducing valve and transported to a solvent flash tower, the alcohol solvent is evaporated from the top of the solvent flash tower and then cooled by a condenser of the solvent flash tower, a part of which is transported to the alcohol solvent storage tank for recycling, and a part of which is discharged as waste liquid, and the concentrated crude hexamethylenediamine solution C flows out from the bottom of the solvent flash tower;

[0024] 2.4) The crude hexamethylenediamine solution C is transported to a cooling crystallizer, and the temperature of the cooling crystallizer is controlled at 25-40° C. by a refrigerant. The hexamethylenediamine product is obtained by cooling and crystallizing and transported to a hexamethylenediamine product storage tank.

[0025] According to certain embodiments of the present invention, in step 1.1), the reaction pressure in the hydroformylation high-gravity reactor is 1.2 MPa-1.5 MPa, the temperature is 80-150° C., and the time is 0.5 h-7 h.

[0026] According to certain embodiments of the present invention, in step 1.1), the rotation speed of the rotor in the hydroformylation high-gravity reactor is 500-1500 r / min.

[0027] According to certain embodiments of the present invention, in step 1.1), the heat exchange temperature of the first heat exchanger is 80-100°C, the heat exchange temperature of the second heat exchanger is 40-60°C, and the heat exchange temperature of the third heat exchanger is 20-50°C;

[0028] According to certain embodiments of the present invention, in step 1.3), the crude adipaldehyde heater is heated to 190-220° C., and the first pressure reducing valve is decompressed to 0.01-0.08 MPa.

[0029] According to certain embodiments of the present invention, in step 1.3), the heat exchange temperature of the condenser of the adipaldehyde flash tower is 30-50°C;

[0030] According to certain embodiments of the present invention, in step 2.1), the reduction amination reaction pressure is controlled at 0.1 MPa-3 MPa, the reaction temperature is 20-80° C., and the reaction time is 0.5 h-3 h.

[0031] According to certain embodiments of the present invention, in step 2.1), the rotor speed in the reduction amination high gravity reactor is 500-1500 r / min;

[0032] According to some embodiments of the present invention, in step 2.3), the second pressure reducing valve reduces the pressure to 0.2 MPa-0.8 MPa.

[0033] According to certain embodiments of the present invention, in step 2.3), the heat exchange temperature of the solvent flash tower condenser is 25-40°C.

[0034] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0035] Unless otherwise specified, all raw materials in the present invention can be purchased from the market, and the equipment used in the present invention can adopt conventional equipment in the relevant field or refer to the existing technology in the relevant field.

[0036] Compared with the prior art, the present invention has the following beneficial effects: :

[0037] 1. The present invention provides a process for producing hexamethylenediamine products from butadiene in a supergravity reactor, which includes two stages: hydroformylation and reductive amination. In the present method, a supergravity reactor with good micro-mixing effect and outstanding gas-liquid mass transfer capacity is used as the reactor for the two key reactions of hydroformylation and reductive amination, which shortens the reaction time and improves the selectivity and conversion rate of the hydroformylation process.

[0038] 2. The present invention uses a three-stage gas-liquid separation device and an adipaldehyde flash tower to circulate the catalyst back to the hydroformylation ultra-gravity reactor or the catalyst raw material tank, so that the catalyst can be recycled; the alcohol solvent is evaporated and circulated back to the alcohol solvent storage tank through the solvent flash tower, so that the material can be recycled and the production cost can be reduced.

[0039] 3. The present invention is different from the traditional process routes of acrylonitrile electrolysis and butadiene hydrocyanation, avoiding the highly toxic hydrocyanic acid gas, sodium cyanide, potassium cyanide, etc. The raw materials used are mild, cheap, easy to obtain, and have abundant reserves, which is in line with the concept and trend of national green development. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0041] Figure 1 The present invention shows a system device and a schematic flow diagram for preparing hexamethylenediamine from butadiene. DETAILED DESCRIPTION

[0042] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0043] Various cross-sectional views of the embodiments disclosed in the present invention are shown in the accompanying drawings. These drawings are not drawn to scale, and some details are magnified and some details may be omitted for the purpose of clear expression. The shapes of various regions and layers shown in the drawings and the relative sizes and positional relationships between them are only exemplary, and may deviate in practice due to manufacturing tolerances or technical limitations, and those skilled in the art may design regions / layers with different shapes, sizes, and relative positions according to actual needs.

[0044] At present, the process routes for synthesizing hexamethylenediamine in industry are mainly divided into two categories. One is to synthesize adiponitrile from raw materials such as acrylonitrile and adipic acid, and then indirectly synthesize hexamethylenediamine from adiponitrile; the other is to directly synthesize hexamethylenediamine from raw materials such as hexamethylenediol and butadiene through conversion, skipping adiponitrile. In the above route, butadiene is hydroformylated to synthesize adipaldehyde, and then adipaldehyde is further aminated and hydrogenated to obtain hexamethylenediamine. The route avoids highly toxic raw materials such as hydrocyanic acid gas, sodium cyanide, potassium cyanide, etc., and the gas raw materials required for the reaction are cheap and easy to obtain. The yield and conversion rate of the amination hydrogenation stage in the process route are also high. It is a potential new industrial method. The reason for the low yield of the final hexamethylenediamine is the low yield of the hydroformylation reaction of conjugated olefins such as butadiene.

[0045] Based on this, as one aspect of the present invention, the present invention provides a system device for preparing hexamethylenediamine from butadiene, comprising:

[0046] Catalyst storage tank 1, catalyst solution delivery pump 2, 1,3-butadiene steel cylinder 3, synthesis gas steel cylinder 4, hydroformylation supergravity reactor 5, first gas-liquid separation tank 6, first heat exchanger 7, second gas-liquid separation tank 8, second heat exchanger 9, third gas-liquid separation tank 10, crude adipaldehyde heater 11, first pressure reducing valve 12, adipaldehyde flash tower 13, adipaldehyde flash tower condenser 14, adipaldehyde buffer tank 15, adipaldehyde delivery pump 16, ammonia steel cylinder 17, hydrogen steel cylinder 18, reduction amination supergravity reactor 19, alcohol solvent storage tank 20, alcohol solvent delivery pump 21, catalyst filter 22, hexamethylenediamine cooler 23, dehydration tower 24, second pressure reducing valve 25, solvent flash tower 26, solvent flash tower condenser 27, cooling crystallizer 28 and hexamethylenediamine product storage tank 29;

[0047] The catalyst storage tank, catalyst solution delivery pump, hydroformylation high gravity reactor, first gas-liquid separation tank, crude adipaldehyde heater, first pressure reducing valve, adipaldehyde flash tower, adipaldehyde flash tower condenser, adipaldehyde buffer tank, adipaldehyde delivery pump, reduction amination high gravity reactor, catalyst filter, hexamethylenediamine cooler, dehydration tower, second pressure reducing valve, solvent flash tower, cooling crystallizer and hexamethylenediamine product storage tank are sequentially connected through pipelines;

[0048] The 1,3-butadiene steel cylinder 3 and the synthesis gas steel cylinder 4 are respectively connected to the hydroformylation high-gravity reactor 5 through pipelines;

[0049] The top of the first gas-liquid separation tank 6 is connected to the inlet of the first heat exchanger 7 through a pipeline, the outlet of the first heat exchanger 7 is connected to the second gas-liquid separation tank 8 through a pipeline, the bottom of the second gas-liquid separation tank 8 is connected to the hydroformylation high gravity reactor 5 through a pipeline, and the top of the second gas-liquid separation tank 8 is connected to the inlet of the second heat exchanger 9 through a pipeline; the outlet of the second heat exchanger 9 is connected to the third gas-liquid separation tank 10 through a pipeline, and the bottom of the third gas-liquid separation tank 10 is connected to the hydroformylation high gravity reactor 5 through a pipeline;

[0050] The ammonia cylinder 17 and the hydrogen cylinder 18 are connected to the reduction ammonia high-gravity reactor 19 through pipelines respectively;

[0051] The top of the solvent flash tower 26 is connected to the solvent flash tower condenser 27 through a pipeline, the solvent flash tower condenser 27 is connected to the alcohol solvent storage tank 20 through a pipeline, the alcohol solvent storage tank 20 is connected to the alcohol solvent delivery pump 21 through a pipeline, and the alcohol solvent delivery pump 21 is connected to the reduction amination supergravity reactor 19 through a pipeline.

[0052] The functions and effects of each component in the present invention are described as follows:

[0053] The catalyst raw material tank 1 is connected to the hydroformylation high gravity reactor 5 and is used to store the catalyst and transport the stored catalyst to the hydroformylation high gravity reactor 5 for hydroformylation reaction;

[0054] The hydroformylation high-gravity reactor 5 is used for carrying out a hydroformylation reaction to prepare adipaldehyde;

[0055] The first, second and third gas-liquid separation tanks 6, 8 and 10, together with the first and second heat exchangers 7 and 9, form a three-stage gas-liquid separation device for separating the crude adipaldehyde solution from gas impurities, and at the same time, the crude adipaldehyde solution containing the catalyst at the bottom of the second and third separation tanks of the separation device is transported to the hydroformylation high gravity reactor 5 for recycling;

[0056] The adipaldehyde flash tower 13 is used to flash adipaldehyde and simultaneously transport a portion of the catalyst solution at the bottom of the tower to the catalyst raw material tank 1 for recycling, and a portion is discharged as waste liquid;

[0057] The alcohol solvent storage tank 20 is connected to the reduction amination high gravity reactor 19, and is used to store the alcohol solvent and transport the stored alcohol solvent to the reduction amination high gravity reactor 19;

[0058] The reductive amination supergravity reactor 19 is used for producing hexamethylenediamine by reductive amination reaction;

[0059] The dehydration tower 24 is filled with molecular sieves to remove water from the cooled crude hexamethylenediamine solution;

[0060] The solvent flash tower 26 is connected to the dehydration tower 24 and is used to evaporate the alcohol solvent in the crude hexamethylenediamine solution, and at the same time, a part of the alcohol solvent is transported to the alcohol solvent storage tank 20 for recycling, and a part is discharged as waste liquid;

[0061] The cooling crystallizer 28 is used to cool and crystallize the crude hexamethylenediamine solution to obtain the hexamethylenediamine product.

[0062] As another aspect of the present invention, a method for preparing hexamethylenediamine from butadiene using the above-mentioned device comprises the following steps:

[0063] 1) Hydroformylation Section

[0064] 1.1) transporting the catalyst and solvent adipaldehyde stored in the catalyst raw material tank, as well as the raw material synthesis gas and 1,3-butadiene to the hydroformylation high-gravity reactor for hydroformylation reaction, and the hydroformylation reaction obtains a crude adipaldehyde solution A;

[0065] 1.2) The crude adipaldehyde solution A after the hydroformylation reaction is completed is sequentially transported to the first gas-liquid separation tank, the second gas-liquid separation tank and the third gas-liquid separation tank through pipelines, and the crude adipaldehyde solution B separated by the first gas-liquid separation tank is sent to the adipaldehyde flash tower for further refining by step-by-step gas-liquid separation and step-by-step cooling by the first heat exchanger and the second heat exchanger, and a small portion of the crude adipaldehyde solution C containing the catalyst separated by the first gas-liquid separation tank, the second gas-liquid separation tank and the third gas-liquid separation tank is transported to the hydroformylation high gravity reactor for continued catalytic reaction, and the mixed gas discharged from the top of the third gas-liquid separation tank is treated as tail gas;

[0066] 1.3) the crude adipaldehyde solution B separated by the first gas-liquid separation tank is heated by a crude adipaldehyde heater, then decompressed by a first pressure reducing valve, and enters an adipaldehyde flash tower for flash evaporation, adipaldehyde is evaporated at the top of the tower, cooled by an adipaldehyde flash tower condenser as an adipaldehyde solution and transported to an adipaldehyde buffer tank, and a part of the crude adipaldehyde solution D containing the catalyst flowing out of the bottom of the tower kettle of the adipaldehyde flash tower is transported to a catalyst raw material tank for recycling, and a part is discharged as waste liquid;

[0067] 2) Reduction ammonia chemical section

[0068] 2.1) transporting the adipaldehyde stored in the adipaldehyde buffer tank, the alcohol solvent and the Raney nickel catalyst stored in the alcohol solvent storage tank, the ammonia stored in the ammonia cylinder, and the hydrogen stored in the hydrogen cylinder to the reduction amination high gravity reactor via pipelines to undergo reduction amination reaction;

[0069] 2.2) After the reduction amination reaction, the crude hexamethylenediamine solution A is filtered through a catalyst filter and then cooled through a hexamethylenediamine cooler, and then transported to a dehydration tower, and subjected to water absorption treatment by a molecular sieve filled in the dehydration tower to obtain a crude hexamethylenediamine solution B;

[0070] 2.3) The crude hexamethylenediamine solution B after dehydration treatment is depressurized by a second pressure reducing valve and transported to a solvent flash tower, the alcohol solvent is evaporated from the top of the solvent flash tower and then cooled by a condenser of the solvent flash tower, a part of which is transported to the alcohol solvent storage tank for recycling, and a part of which is discharged as waste liquid, and the concentrated crude hexamethylenediamine solution C flows out from the bottom of the solvent flash tower;

[0071] 2.4) The crude hexamethylenediamine solution C is transported to a cooling crystallizer, and the temperature of the cooling crystallizer is controlled at 25-40° C. by a refrigerant. The hexamethylenediamine product is obtained by cooling and crystallizing and transported to a hexamethylenediamine product storage tank.

[0072] According to certain embodiments of the present invention, in step 1.1), the reaction pressure in the hydroformylation high-gravity reactor is 1.2 MPa-1.5 MPa, the temperature is 80-150° C., and the time is 0.5 h-7 h.

[0073] According to certain embodiments of the present invention, in step 1.1), the rotation speed of the rotor in the hydroformylation high-gravity reactor is 500-1500 r / min.

[0074] According to certain embodiments of the present invention, in step 1.1), the heat exchange temperature of the first heat exchanger is 80-100°C, the heat exchange temperature of the second heat exchanger is 40-60°C, and the heat exchange temperature of the third heat exchanger is 20-50°C;

[0075] According to certain embodiments of the present invention, in step 1.3), the crude adipaldehyde heater is heated to 190-220° C., and the first pressure reducing valve is decompressed to 0.01-0.08 MPa.

[0076] According to certain embodiments of the present invention, in step 1.3), the heat exchange temperature of the condenser of the adipaldehyde flash tower is 30-50°C;

[0077] According to certain embodiments of the present invention, in step 2.1), the reduction amination reaction pressure is controlled at 0.1 MPa-3 MPa, the reaction temperature is 20-80° C., and the reaction time is 0.5 h-3 h.

[0078] According to certain embodiments of the present invention, in step 2.1), the rotor speed in the reduction amination high gravity reactor is 500-1500 r / min;

[0079] According to some embodiments of the present invention, in step 2.3), the second pressure reducing valve reduces the pressure to 0.2 MPa-0.8 MPa.

[0080] According to certain embodiments of the present invention, in step 2.3), the heat exchange temperature of the solvent flash tower condenser is 25-40°C.

[0081] Example 1

[0082] A method for preparing hexamethylenediamine from butadiene using a supergravity reactor comprises the following steps:

[0083] 50g of acetylacetonato triphenylphosphine carbonyl rhodium and 200g of ligand triphenylphosphine were dissolved in 100L of 1,6-hexanedial solvent to prepare a catalyst solution. The catalyst solution stored in the catalyst raw material tank was pumped into the hydroformylation supergravity reactor at a flow rate of 2L / h, and 1,3-butadiene was transported from a steel cylinder to the hydroformylation supergravity reactor via a pipeline, with a 1,3-butadiene flow rate of 2L / min; the volume ratio of hydrogen to carbon monoxide in the synthesis gas was 1:1; the synthesis gas was continuously introduced to control the pressure in the reactor at 1.3MPa, and the temperature in the supergravity reactor was controlled at 85°C by a heat medium for hydroformylation reaction. The speed of the supergravity reactor was 1200r / min, and the reaction time was 4h. The hydroformylation reaction obtained a crude hexanedial solution A;

[0084] The crude adipaldehyde solution A after the hydroformylation reaction is completed is transported to a three-stage gas-liquid separation device through a pipeline, and the crude adipaldehyde solution B obtained by separation in the first gas-liquid separation tank is sent to an adipaldehyde flash tower for further refining by means of step-by-step gas-liquid separation and cooling. A small portion of the crude adipaldehyde solution C containing the catalyst obtained by separation in the second gas-liquid separation tank and the third gas-liquid separation tank is transported to a hydroformylation high-gravity reactor for continued catalytic reaction, and the mixed gas discharged from the top of the third gas-liquid separation tank is treated as tail gas;

[0085] The crude adipaldehyde solution B which has passed through the three-stage gas-liquid separation device is heated to 200° C. by a crude adipaldehyde heater, then decompressed to 0.01-0.08 MPa by a pressure reducing valve, and enters an adipaldehyde flash tower for flash evaporation. The adipaldehyde is evaporated at the top of the tower, cooled to an adipaldehyde solution by an adipaldehyde flash tower condenser, and enters an adipaldehyde buffer tank. A portion of the crude adipaldehyde solution C containing the catalyst flowing out of the bottom of the tower is transported to a catalyst raw material tank for recycling, and a portion is discharged as waste liquid;

[0086] The adipaldehyde stored in the adipaldehyde buffer tank is pumped to the reduction amination reactor at a flow rate of 0.5L / h, 100g of Raney nickel catalyst is placed in 100L ethanol and stored in an alcohol solvent tank, and the ethanol solvent containing the Raney nickel catalyst is pumped to the reduction amination reactor at a flow rate of 3L / h. The raw ammonia and hydrogen volume ratio is 1:1, and both are transported to the reduction amination supergravity reactor through a pipeline to maintain the pressure at 0.1MPa-3MPa, the speed of the supergravity reactor is 1200r / min, and the temperature in the supergravity reactor is controlled at 20℃ for reduction amination reaction, and the reaction time is 2h;

[0087] The crude hexamethylenediamine solution A after the reduction amination reaction is filtered, cooled, and then transported to a dehydration tower, and subjected to water absorption treatment by a molecular sieve filled in the dehydration tower to obtain a crude hexamethylenediamine solution B;

[0088] The crude hexamethylenediamine solution B after dehydration treatment is depressurized to 0.2MPa-0.8MPa through a pressure reducing valve and transported to a solvent flash tower, the alcohol solvent is evaporated from the top of the tower and then cooled by a condenser of the solvent flash tower, a part of which enters the alcohol solvent tank for recycling, and a part of which is discharged as waste liquid, while the concentrated crude hexamethylenediamine solution C flows out from the bottom of the tower;

[0089] The crude hexamethylenediamine solution C obtained from the solvent flash tower kettle is transported to a cooling crystallizer, and the temperature of the cooling crystallizer is controlled at 30°C by a refrigerant. The hexamethylenediamine product is obtained by cooling and crystallizing and transported to a hexamethylenediamine product storage tank.

[0090] By comparison, the reaction time of the present invention is shortened to 0.1-0.7 times of the original one compared with conventional reactors such as stirred tanks, the conversion rate of 1,3-butadiene in the hydroformylation process is 91.2%, and the selectivity of adipaldehyde is 53%.

[0091] Example 2

[0092] A method for preparing hexamethylenediamine from butadiene using a supergravity reactor comprises the following steps:

[0093] 5g of acetylacetonato triphenylphosphine carbonyl rhodium, 100g of ligand diphenylphosphine propionic acid, and 10g of p-tert-butylcatechol were dissolved in 100L of 1,6-hexanedial solvent to prepare a catalyst solution. The catalyst solution stored in the catalyst raw material tank was pumped into the hydroformylation supergravity reactor at a flow rate of 2L / h, and 1,3-butadiene was transported from a steel cylinder to the hydroformylation supergravity reactor via a pipeline, with a 1,3-butadiene flow rate of 2L / min; the volume ratio of hydrogen to carbon monoxide in the synthesis gas was 1:1; the synthesis gas was continuously introduced to control the pressure in the reactor at 1.5MPa, and the temperature in the supergravity reactor was controlled at 120℃ by a heat medium for hydroformylation reaction, the speed of the supergravity reactor was 1500r / min, the reaction time was 2.5h, and the hydroformylation reaction obtained a crude hexanedial solution A;

[0094] The crude adipaldehyde solution A after the hydroformylation reaction is completed is transported to a three-stage gas-liquid separation device through a pipeline, and the crude adipaldehyde solution B obtained by separation in the first gas-liquid separation tank is sent to an adipaldehyde flash tower for further refining by means of step-by-step gas-liquid separation and cooling. A small portion of the crude adipaldehyde solution C containing the catalyst obtained by separation in the second gas-liquid separation tank and the third gas-liquid separation tank is transported to a hydroformylation high-gravity reactor for continued catalytic reaction, and the mixed gas discharged from the top of the third gas-liquid separation tank is treated as tail gas;

[0095] The crude adipaldehyde solution B which has passed through the three-stage gas-liquid separation device is heated to 190° C. by a crude adipaldehyde heater, then reduced to 0.01-0.08 MPa by a pressure reducing valve, and enters an adipaldehyde flash tower for flash evaporation. The adipaldehyde is evaporated at the top of the tower, cooled to an adipaldehyde solution by an adipaldehyde flash tower condenser, and enters an adipaldehyde buffer tank. A portion of the crude adipaldehyde solution C containing the catalyst flowing out of the bottom of the tower is transported to a catalyst raw material tank for recycling, and a portion is discharged as waste liquid;

[0096] The adipaldehyde stored in the adipaldehyde buffer tank is pumped to the reduction amination reactor at a flow rate of 0.5L / h, 50g of Raney nickel catalyst and 20g of acetic acid are placed in 100L of butanol and stored in an alcohol solvent tank, and the butanol solvent containing the Raney nickel catalyst is pumped to the reduction amination reactor at a flow rate of 3L / h. The raw ammonia and hydrogen volume ratio is 1:1, and both are transported to the reduction amination supergravity reactor through a pipeline to maintain the pressure at 0.1MPa-3MPa, the speed of the supergravity reactor is 1500r / min, and the temperature in the supergravity reactor is controlled at 45℃ for reduction amination reaction, and the reaction time is 1h;

[0097] The crude hexamethylenediamine solution A after the reduction amination reaction is filtered, cooled, and then transported to a dehydration tower, and subjected to water absorption treatment by a molecular sieve filled in the dehydration tower to obtain a crude hexamethylenediamine solution B;

[0098] The crude hexamethylenediamine solution B after dehydration treatment is depressurized to 0.2MPa-0.8MPa through a pressure reducing valve and transported to a solvent flash tower, the alcohol solvent is evaporated from the top of the tower and then cooled by a condenser of the solvent flash tower, a part of which enters the alcohol solvent tank for recycling, and a part of which is discharged as waste liquid, while the concentrated crude hexamethylenediamine solution C flows out from the bottom of the tower;

[0099] The crude hexamethylenediamine solution C obtained from the solvent flash tower kettle is transported to a cooling crystallizer, and the temperature of the cooling crystallizer is controlled at 25°C by a refrigerant. The hexamethylenediamine product is obtained by cooling and crystallizing and transported to a hexamethylenediamine product storage tank.

[0100] By comparison, the reaction time of the present invention is shortened to 0.1-0.7 times of the original one compared with conventional reactors such as stirred tanks, the conversion rate of 1,3-butadiene in the hydroformylation process is 88.6%, and the selectivity of adipaldehyde is 55%.

[0101] Obviously, the above embodiments of the present invention are merely examples for clearly explaining the present invention, and are not intended to limit the implementation methods of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all implementation methods here. Any obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A system for preparing hexamethylenediamine from butadiene, characterized in that: include: Catalyst storage tank, catalyst solution delivery pump, 1,3-butadiene steel cylinder, synthesis gas steel cylinder, hydroformylation supergravity reactor, first gas-liquid separation tank, first heat exchanger, second gas-liquid separation tank, second heat exchanger, third gas-liquid separation tank, crude adipaldehyde heater, first pressure reducing valve, adipaldehyde flash tower, adipaldehyde flash tower condenser, adipaldehyde buffer tank, adipaldehyde delivery pump, ammonia steel cylinder, hydrogen steel cylinder, reduction amination supergravity reactor, alcohol solvent storage tank, alcohol solvent delivery pump, catalyst filter, hexamethylenediamine cooler, dehydration tower, second pressure reducing valve, solvent flash tower, solvent flash tower condenser, cooling crystallizer and hexamethylenediamine product storage tank; The catalyst storage tank, catalyst solution delivery pump, hydroformylation high gravity reactor, first gas-liquid separation tank, crude adipaldehyde heater, first pressure reducing valve, adipaldehyde flash tower, adipaldehyde flash tower condenser, adipaldehyde buffer tank, adipaldehyde delivery pump, reduction amination high gravity reactor, catalyst filter, hexamethylenediamine cooler, dehydration tower, second pressure reducing valve, solvent flash tower, cooling crystallizer and hexamethylenediamine product storage tank are sequentially connected through pipelines; The 1,3-butadiene steel cylinder and the synthesis gas steel cylinder are respectively connected to the hydroformylation high-gravity reactor through pipelines; The top of the first gas-liquid separation tank is connected to the inlet of the first heat exchanger through a pipeline, the outlet of the first heat exchanger is connected to the second gas-liquid separation tank through a pipeline, the bottom of the second gas-liquid separation tank is connected to the hydroformylation high-gravity reactor through a pipeline, and the top of the second gas-liquid separation tank is connected to the inlet of the second heat exchanger through a pipeline; the outlet of the second heat exchanger is connected to the third gas-liquid separation tank through a pipeline, and the bottom of the third gas-liquid separation tank is connected to the hydroformylation high-gravity reactor through a pipeline; The ammonia gas cylinder and the hydrogen gas cylinder are respectively connected to the reduction ammonia high-gravity reactor through pipelines; The top of the solvent flash tower is connected to the solvent flash tower condenser through a pipeline, the solvent flash tower condenser is connected to the alcohol solvent storage tank through a pipeline, the alcohol solvent storage tank is connected to the alcohol solvent delivery pump through a pipeline, and the alcohol solvent delivery pump is connected to the reduction amination supergravity reactor through a pipeline.

2. A method for preparing hexamethylenediamine from butadiene using the apparatus as claimed in claim 1, characterized in that: The steps include: 1) Hydroformylation Chemical Industry Section 1.1) The catalyst and solvent adipaldehyde stored in the catalyst raw material tank, as well as the raw material synthesis gas and 1,3-butadiene are transported to the hydroformylation ultra-gravity reactor to undergo a hydroformylation reaction, and the hydroformylation reaction obtains a crude adipaldehyde solution A; 1.2) The crude adipaldehyde solution A after the hydroformylation reaction is completed is sequentially transported to the first gas-liquid separation tank, the second gas-liquid separation tank and the third gas-liquid separation tank through pipelines, and the crude adipaldehyde solution B separated by the first gas-liquid separation tank is sent to the adipaldehyde flash tower for further refining by means of step-by-step gas-liquid separation and step-by-step cooling by the first heat exchanger and the second heat exchanger, and a small portion of the crude adipaldehyde solution C containing the catalyst separated by the first gas-liquid separation tank, the second gas-liquid separation tank and the third gas-liquid separation tank is transported to the hydroformylation high gravity reactor for further catalytic reaction, and the mixed gas discharged from the top of the third gas-liquid separation tank is treated as tail gas; 1.3) The crude adipaldehyde solution B separated in the first gas-liquid separation tank is heated by a crude adipaldehyde heater, then decompressed by a first pressure reducing valve, and enters an adipaldehyde flash tower for flash evaporation. The adipaldehyde is evaporated at the top of the tower, cooled by an adipaldehyde flash tower condenser to be an adipaldehyde solution, and transported to an adipaldehyde buffer tank. A portion of the crude adipaldehyde solution D containing the catalyst flowing out of the bottom of the tower kettle of the adipaldehyde flash tower is transported to a catalyst raw material tank for recycling, and a portion is discharged as waste liquid; 2) Reduction ammonia chemical section 2.1) transporting the adipaldehyde stored in the adipaldehyde buffer tank, the alcohol solvent and the Raney nickel catalyst stored in the alcohol solvent storage tank, the ammonia stored in the ammonia cylinder, and the hydrogen stored in the hydrogen cylinder to the reduction amination high gravity reactor via pipelines to undergo reduction amination reaction; 2.2) After the reduction amination reaction, the crude hexamethylenediamine solution A is filtered through a catalyst filter and then cooled through a hexamethylenediamine cooler and then transported to a dehydration tower, and subjected to water absorption treatment by a molecular sieve filled in the dehydration tower to obtain a crude hexamethylenediamine solution B; 2.3) The crude hexamethylenediamine solution B after dehydration treatment is depressurized by the second pressure reducing valve and transported to the solvent flash tower, the alcohol solvent is evaporated from the top of the solvent flash tower and then cooled by the condenser of the solvent flash tower, a part of which is transported to the alcohol solvent storage tank for recycling, and a part is discharged as waste liquid, and the concentrated crude hexamethylenediamine solution C flows out from the bottom of the solvent flash tower; 2.4) The crude hexamethylenediamine solution C is transported to a cooling crystallizer, and the temperature of the cooling crystallizer is controlled at 25-40°C by a refrigerant. The hexamethylenediamine product is obtained by cooling and crystallizing and transported to a hexamethylenediamine product storage tank; In step 1.1), the reaction pressure in the hydroformylation high gravity reactor is 1.2MPa-1.5MPa, the temperature is 80-150°C, and the time is 0.5h-7h; In step 1.1), the rotor speed in the hydroformylation high-gravity reactor is 500-1500 r / min; In step 1.2), the heat exchange temperature of the first heat exchanger is 80-100°C, and the heat exchange temperature of the second heat exchanger is 40-60°C; In step 1.3), the crude adipaldehyde heater is heated to 190-220° C., and the first pressure reducing valve is decompressed to 0.01-0.08 MPa; In step 1.3), the heat exchange temperature of the condenser of the adipaldehyde flash tower is 30-50°C; In step 2.1), the reduction amination reaction pressure is controlled at 0.1 MPa-3 MPa, the reaction temperature is 20-80°C, and the reaction time is 0.5h-3h; In step 2.1), the rotor speed in the reduction amination high gravity reactor is 500-1500 r / min; In step 2.3), the second pressure reducing valve reduces the pressure to 0.2MPa-0.8MPa; In step 2.3), the heat exchange temperature of the solvent flash tower condenser is 25-40°C.

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