METHOD AND DEVICE FOR PREPARING DIISOCYANATE

Abstract

A tubular reactor comprises a tubular shell, an external jacket, and a gas distribution device at the top of the shell, wherein at least one group of feed nozzles are distributed uniformly on the shell, each group comprising at least one phosgene nozzle and at least one diamine nozzle; a reaction material is sprayed through the nozzles and impinges with each other in a middle impingement zone to strengthen the reaction effect, the gas distribution device is arranged at the top of the shell and the upper part of the feed nozzle, and an inert medium distributed uniformly through the gas distribution device is refracted at the top of the shell into an impingement reaction zone, so as to reduce the temperature and concentration of the reaction zone.

Claims

1. A method for preparing diisocyanate, comprising: a first section of reactor—rapid reaction heat transfer section: a) heating and gasifying phosgene and diamine respectively, with the reaction temperature of 200-300° C. in a feed nozzle; b) heating an inert medium in a gas distribution device, with the refraction temperature of the inert medium of 150-250° C. at the top of a shell; c) effectively micromixing phosgene and diamine distributed through the nozzles in an impingement zone, with the inert medium passing through the impingement reaction zone from above to take away excess heat, and a gas phase mixture passing through the impingement mixing reaction zone and setting off a further reaction along a tubular reactor, indicating that a reaction system enters a second section—slow reaction heat preservation section; and a second section of reactor—slow reaction heat preservation section: d) obtaining a gas-phase diisocyanate mixture at the slow reaction heat preservation section, circularly absorbing a crude diisocyanate mixture by a solvent in a quenching zone to obtain a liquid-phase crude product, and removing light/heavy components in a rectifying tower to obtain a diisocyanate product, with the gas entering a tail gas treatment device for absorption and recycling.

2. The method according to claim 1, wherein the inert medium contained in the gas distribution device is a mixture of one or more of nitrogen, argon, helium, radon, carbon dioxide and carbon monoxide.

3. The method according to claim 1, wherein the molar ratio of amine to phosgene is 1:1.2-5, preferably 1:1.3-4, more preferably 1:1.5-3, even more preferably 1:1.6-2, and most preferably 1:1.8-2.

4. The method according to claim 1, wherein diamine is selected from toluenediamine, methylene diphenyl amine, 1,6-hexanediamine, isophorone diamine, cyclohexane diamine, 1,4-butanediamine, 1,5-diamino-2-methylpentane, 1,4-diaminocyclohexane, m-phenylenedimethylene diamine, 4,4′-diaminodicyclohexylmethane, diaminobenzene and naphthalene diamine.

5. A low-temperature gas phase reactor for preparing diisocyanate, comprising: an upper rapid reaction heat transfer section and a lower slow reaction heat preservation section, wherein both sections are jacketed-tube reactors having respective independent jacketed devices and supporting independent temperature control; the upper rapid reaction heat transfer section (3) comprises a tubular shell (6), a sectional jacket (7) arranged on the outside thereof, and a gas distribution device (1) arranged at the top of the shell; at least one group of feed nozzles are distributed uniformly and horizontally on the shell, each group comprising at least one phosgene nozzle (21) and at least one diamine nozzle (22); a reaction material is sprayed through the nozzles and impinges with each other in a middle impingement zone, arranged below is a disc (10) with a diameter smaller than the inner diameter of the tubular reactor, which serves to prevent the mixture from directly entering the reaction section, resulting a turbulent reaction mixture, and adjust the contact time between phosgene and amine, and is connected to a rotating shaft (4) so that a gas mixture goes down along the reactor wall; a fan blade (5) is arranged on the rotating shaft and is rotated to quickly guide reactants into the lower section; the gas distribution device (1) is arranged at the top of the shell and the upper part of the feed nozzle, an air outlet device is arranged at the upper surface of the gas distribution device, and the inert medium distributed uniformly through the gas distribution device is refracted at the top of the shell to the impingement reaction zone to reduce the temperature and concentration of the reaction zone; the sectional jacket arranged on the outside of the tubular shell contains a heat transfer medium for effectively controlling the shell wall temperature; the lower slow reaction heat preservation section is much the same as the upper rapid reaction heat transfer section, except that no gas distribution device or a feed nozzle is arranged, and the rotating shaft rotates reversely; the upper section and the lower section are connected by check valves (8) and (9); the outlet of the lower section is connected to the quenching zone, the rectifying tower and the tail gas treatment device; phosgene and diamine feeding into the shell are dispersed through nozzles, with a disperse phase impinging between two feed pipes; a turbulent impingement zone produced by the impinging stream is located in a steady-state impingement zone between the two feed pipes, with a diameter of the turbulent impingement zone of d1=(0.2-0.6) D, and a diameter of the disc (10) of d2=(0.6-0.9) D, and D of 0.5-1 m, where D is the inner diameter of the tubular shell; the disc is 10-100 mm from the plane of the impingement zone formed by the nozzles; the gas distribution device is selected from one of slotted disc type, tubular type, lift cap type and vane type, and is 10-100 mm from the top of the tubular shell and 10-200 mm from the steady-state impingement zone; the sectional jacket arranged on the outside of the tubular shell contains a heat transfer medium, and the heat transfer medium in the jackets of the upper and lower sections are independently selected from one of heat transfer oil, steam and molten salt; the length of the upper rapid reaction heat transfer section is 500-2000 mm and that of the lower slow reaction heat preservation section is 1000-7000 mm.

6. The reactor according to claim 5, wherein the tubular shell is provided with 1-4 phosgene nozzles and 1-4 diamine nozzles, preferably 2-3 phosgene nozzles and 2-3 diamine nozzles, wherein the phosgene nozzles and the diamine nozzles are alternately, uniformly, symmetrically and horizontally distributed on the reactor shell at intervals, and the number of phosgene nozzles is preferably the same as that of the diamine nozzles, preferably 2.

7. A method for preparing diisocyanate, wherein diisocyanate is prepared by the reactor of claim 5 according to the method claimed in claim 1.

8. The method according to claim 7, wherein phosgene and diamine are fed into the impingement zone via the phosgene and diamine nozzles at the same speed of 10-50 m/s; the average residence time of phosgene and diamine in the impingement zone is 0.01-0.5 s; the inert medium uniformly distributed through the gas distribution device is refracted to the impingement reaction zone at the top of the shell at 0.1-8 m/s, and the reaction pressure in the upper and lower tubular reactors is 0.2-10 bar.

9. The method according to claim 7, wherein the quenching zone is a scrubbing tower, a quenching solvent is selected from one of chlorobenzene, dichlorobenzene or isocyanate, and the quenching temperature is 100-200° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0041] FIG. 1 is a schematic diagram of the reactor with a single-group feed nozzle.

[0042] FIG. 2 shows the structural arrangement of the feed nozzle.

[0043] FIG. 3 is a schematic diagram of the reactor with a double-group feed nozzle.

[0044] The numbers in the figure indicate as follows: 1—gas distribution device, 21—phosgene nozzle, 22—diamine nozzle, 3—reactor, 4—rotating shaft, 5—flow promoting blade, 6—reactor shell, 7—sectional jacket arranged on the outside of the tubular shell—upper rapid reaction heat transfer section, 8 and 9—device connecting upper rapid reaction heat transfer section and lower slow reaction heat preservation section of reactor, 10—disc.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0045] The present invention is further described with reference to embodiments and drawings for a clear understanding of the purpose, technical solution and advantages of the present invention. It should be understood that the specific embodiments described herein are for the purpose of describing the present invention only and are not intended to be limiting of the present invention.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. The terms used in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention.

[0047] The reactor for preparing diisocyanate is shown in FIGS. 1-2. In the tubular reactor 3, a phosgene feed pipe 21 enters the reaction pipe in the upper area of thereof and a diamine feed pipe 22 is introduced on the corresponding side of the same position. The central area of the two feed pipes is the reaction impingement zone that is kept in steady state through the continuous and stable feed, and where phosgene and diamine impinge and mix with each other to set off a reaction.

[0048] Wherein, a gas distribution device 1 is arranged on the top of the tubular shell. After passing through the gas distribution device, the inert gas from the feed pipe is evenly distributed on the top of the tubular shell, and then refracted again to the impingement reaction zone, so as to reduce the temperature and concentration of the reaction zone. The outer shell of the tubular reactor is provided with a jacket, comprising an upper part and a lower part, which achieve heat transfer at different temperature. The upper part is a rapid reaction heat transfer section 7, and the lower part is a slow reaction heat preservation section (not shown) which is structurally the same as the upper section largely, except that no gas distribution device or feed device is provided.

[0049] Wherein, a crude diisocyanate gas phase is obtained through the reaction in a tubular reactor, and reaches a quenching zone, where the crude diisocyanate mixture is circularly absorbed by a solvent to obtain a crude diisocyanate product that is sent to a product refining and rectifying tower to remove light and heavy components and obtain a diisocyanate product, while the gas component enters a tail gas treatment device for absorption and recycling.

[0050] FIG. 3 is a reactor with two groups of feed nozzles shown in FIG. 2.

Example 1

[0051] The reactor shown in FIGS. 1-2 was used. The tubular shell was provided with 2 phosgene nozzles and 2 diamine nozzles that were alternately, uniformly and horizontally arranged at intervals, with the axial angle of 90° between the planes where the two adjacent groups of feed nozzles were located. Wherein, the diameter of the impingement reaction zone was d1=0.6 D, and phosgene and diamine entered the impingement zone at a speed of 20 m/s and 20 m/s, respectively. The diameter of the disc was d2=0.7 D and the disc was 100 mm from the impingement zone. The average residence time of the two materials in the impingement zone was 0.2 s and D was 0.5 m. The distance between the tubular gas distribution device and the top of the tubular shell was 80 mm, and the distance between the tubular gas distribution device and the steady-state impingement zone was 100 mm. The inert medium was nitrogen and was refracted to the impingement reaction zone at 4 m/s. The upper rapid reaction heat transfer section of the tubular shell maintained the shell wall temperature of 280° C., and the length of the heat transfer section was 1500 mm. The lower slow reaction heat preservation section maintained the shell wall temperature of 200° C., and the length of the heat preservation section was 6000 mm. The jacket medium was heat transfer oil.

[0052] Preparation of Diisocyanate HDI (1,6-Hexamethylene Diisocyanate)

[0053] 1,6-hexamethylenediamine (HDA) and phosgene were preheated to 250° C., and nitrogen was preheated to 200° C. The nozzle diameter was adjusted and the molar ratio of HDA to phosgene was controlled to be 1:1.5. Phosgene and HDA distributed through the nozzles were effectively micro-mixed in the impingement zone, with nitrogen passing through the impingement reaction zone from above to take away excess heat. A gas phase mixture passing through the impingement mixing reaction zone set off a further reaction along the tubular reactor to obtain a gas-phase diisocyanate mixture, wherein the reaction pressure in the tubular reactor was 1 bar. Then a crude diisocyanate mixture was circularly absorbed by a solvent at 130° C. in a quenching zone to obtain a liquid-phase crude product that was sent to a rectifying tower to remove light/heavy components and obtain a diisocyanate product, while gas components entered a tail gas treatment device.

[0054] In this example, the content of HDI product obtained by the rectifying tower was 99.8%, the chroma was not more than 12 HAZEN (Apha) (far lower than that of commercial products), and the HDA conversion rate was 98.9%. The device was shut down for maintenance after a long period of operation, for example, one month of operation. The results showed that no obvious coking materials were seen at the outlet of the phosgene and diamine feed pipes and the inner wall of the tubular reactor, and the device was in good condition and did not affect the continued reaction.

Example 2

[0055] The reactor shown in FIGS. 1-2 was used. The tubular shell was provided with 2 phosgene nozzles and 2 diamine nozzles that were alternately, uniformly and horizontally arranged at intervals, with the axial angle of 45° between the planes where the two adjacent groups of feed nozzles were located. Wherein, the diameter of the impingement reaction zone was d1=0.65 D, and phosgene and diamine entered the impingement zone at a speed of 18 m/s and 18 m/s, respectively. The average residence time of the two materials in the impingement zone was 0.3 s and D was 0.7 m. The distance between the tubular gas distribution device and the top of the tubular shell was 60 mm, and the distance between the tubular gas distribution device and the steady-state impingement zone was 200 mm. The inert medium was nitrogen and was refracted to the impingement reaction zone at 4 m/s. The upper rapid reaction heat transfer section of the tubular shell maintained the shell wall temperature of 280° C., and the length of the heat transfer section was 1200 mm. The lower slow reaction heat preservation section maintained the shell wall temperature of 220° C., and the length of the heat preservation section was 5000 mm. The jacket medium was heat transfer oil.

[0056] Preparation of Diisocyanate IPDI (Isophorone Diisocyanate)

[0057] Isophorone diamine (IPDA) and phosgene were preheated to 260° C., and nitrogen was preheated to 170° C. The nozzle diameter was adjusted and the molar ratio of IPDA to phosgene was controlled to be 1:1.3. Phosgene and IPDA distributed through the nozzles were effectively micro-mixed in the impingement zone, with nitrogen passing through the impingement reaction zone from above to take away excess heat. A gas phase mixture passing through the impingement mixing reaction zone set off a further reaction along the tubular reactor to obtain a gas-phase diisocyanate mixture, wherein the reaction pressure in the tubular reactor was 1.5 bar. Then a crude diisocyanate mixture was circularly absorbed by a solvent chlorobenzene at 130° C. in a quenching zone to obtain a liquid-phase crude product that was sent to a rectifying tower to remove light/heavy components and obtain a diisocyanate product, while gas components entered a tail gas treatment device.

[0058] In this example, the content of IPDI product obtained by the rectifying tower was 99.5%, the chroma was not more than 20 HAZEN (Apha) (far lower than that of commercial products), and the IPDA conversion rate was 98.9%. The device was shut down for maintenance after three months of operation. The results showed that no obvious coking materials were seen at the outlet of the phosgene and diamine feed pipes and the inner wall of the tubular reactor, and the device was in good condition and did not affect the continued reaction.

Example 3

[0059] The reactor shown in FIGS. 2-3 was used. The tubular shell was provided with 2 phosgene nozzles and 2 diamine nozzles that were alternately, uniformly and horizontally arranged at intervals, with the axial angle of 90° between the planes where the two adjacent groups of feed nozzles are located. The components shown in FIG. 2 were in two groups, with the second group located in the middle section of the reactor. Wherein, the diameter of the impingement reaction zone was d1=0.6 D, and phosgene and diamine entered the impingement zone at a speed of 30 m/s and 30 m/s, respectively. The diameter of the disc was d2=0.6 D and the disc was 100 mm from the impingement zone. The average residence time of the two materials in the impingement zone was 0.3 s and D was 1 m. The distance between the tubular gas distribution device and the top of the tubular shell was 80 mm, and the distance between the tubular gas distribution device and the steady-state impingement zone was 100 mm. The inert medium was nitrogen and was refracted to the impingement reaction zone at 8 m/s. The upper rapid reaction heat transfer section of the tubular shell maintained the shell wall temperature of 280° C., and the length of the heat transfer section was 2000 mm. The lower slow reaction heat preservation section maintained the shell wall temperature of 220° C., and the length of the heat preservation section was 7000 mm. The jacket medium was heat transfer oil.

[0060] Preparation of Diisocyanate IPDI (Isophorone Diisocyanate)

[0061] Isophorone diamine (IPDA) and phosgene were preheated to 260° C., and nitrogen was preheated to 170° C. The nozzle diameter was adjusted and the molar ratio of IPDA to phosgene was controlled to be 1:1.3. Phosgene and IPDA distributed through the nozzles were effectively micro-mixed in the impingement zone, with nitrogen passing through the impingement reaction zone from above to take away excess heat. A gas phase mixture passing through the impingement mixing reaction zone set off a further reaction along the tubular reactor to obtain a gas-phase diisocyanate mixture, wherein the reaction pressure in the tubular reactor was 3 bar. Then a crude diisocyanate mixture was circularly absorbed by a solvent chlorobenzene at 130° C. in a quenching zone to obtain a liquid-phase crude product that was sent to a rectifying tower to remove light/heavy components and obtain a diisocyanate product, while gas components entered a tail gas treatment device.

[0062] In this example, the content of IPDI product obtained by the rectifying tower was 99.6%, the chroma was not more than 21 HAZEN (Apha) (far lower than that of commercial products), and the IPDA conversion rate was 99.1%. The device was shut down for maintenance after two months of operation. The results showed that no obvious coking materials were seen at the outlet of the phosgene and diamine feed pipes and the inner wall of the tubular reactor, and the device was in good condition and did not affect the continued reaction.

[0063] Unrestricted combination of technical features of the above embodiments is accepted. For the sake of brevity, not all possible combinations of the technical features of the above embodiments are described herein; however, the combination of these technical features without any contradictions shall be considered as falling within the scope of the specification.

[0064] The above embodiments of the present invention are not to be construed as limiting of the patent scope of the present invention, despite specific and detailed description. It should be pointed out that, for a person of ordinary skill in the art, a number of variations and improvements can be made without departing from the conception of the present invention, and shall fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for invention shall be subject to the appended claims.