CN101670263B - Reactor for preparing toluene diisocynate by gaseous phase method and operation method - Google Patents
Reactor for preparing toluene diisocynate by gaseous phase method and operation method Download PDFInfo
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- CN101670263B CN101670263B CN2009103065191A CN200910306519A CN101670263B CN 101670263 B CN101670263 B CN 101670263B CN 2009103065191 A CN2009103065191 A CN 2009103065191A CN 200910306519 A CN200910306519 A CN 200910306519A CN 101670263 B CN101670263 B CN 101670263B
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Abstract
The invention relates to a reactor for preparing toluene diisocynate by a gaseous phase method and an operation method. The reactor is of a tubular reactor (8), wherein a central injector is arranged in the middle of the tubular reactor and provided with a cone-shaped deflection baffle and a nozzle; and a deflection baffle is arranged on the pipe wall of the tubular reactor. Charging air current A passes through an inlet (1) of the central injector (9) and enters the tubular reactor (8); charging air current B passes through an inlet (3) of the tubular reactor (8) and enters an annular space (4) between the central injector (9) and the tubular reactor (8); and air current A and air current B are two reactive materials. The invention provides the reactor or preparing toluene diisocynate by the gaseous phase method and the operation method so that air reactant is turbulent in lower flow velocity, prompts the mixed range of the reactant to be shortened, thus reducing the time of the reactant retained in the reactor and the generation of the solid deposition on the wall of the reactor.
Description
Technical field
The invention belongs to field of chemical technology, particularly relate to the reactor and the method for operating of preparing toluene diisocynate by gaseous phase method.
Background technology
Polyurethane is one of the world six synthetic material of having development prospect greatly, has characteristics such as wear-resisting, low temperature resistant, oil resistant and anti-ozone, is widely used in foamed plastics, elastomer, adhesive, coating and fiber etc.And as the toluene di-isocyanate(TDI) of one of polyurethane industrial primary raw material, excellent properties that has with himself and extensive use become the staple product in the isocyanate compound.
The production of toluene diisocyanate method can be divided into phosgenation and non-phosgene, and phosgenation can be divided into liquid phase phosgenation and gas phase phosgenation reaction technology again, and non-phosgene has potential technical advantage, in the industry at present all is to adopt phosgenation to produce isocyanates.Problems such as the cycle of operation that the existence of liquid phase phosgenation reactor causes owing to solid stops up is short, single covering device production capacity is low.Advantages such as the gas phase phosgenation technology has the reaction yield height, the consersion unit investment is little, production efficiency is big, safe and reliable.Light phosgenation prepares the key reaction that comprises among the TDI to be had:
RNH
2+COCl
2→RNHCOCl+HCl
RNH
2+HCl→RNH2HCl
RNHCOCl→RNCO+HCl
RNH
2HCl+COCl
2→RNCO+HCl
In the existing gas phase phosgenation technology, the preparation method of the described isocyanates of US-A-5391683 is that aromatic diamine and phosgene carry out in tubular reactor, and this reactor tube narrows down along the longitudinal axis of reactor, but inside does not have moving assembly.Yet this method utilizes pipeline to narrow down to impel the mixing of raw material, and its effect is relatively poor, and bad mixing is prone to cause the formation of a large amount of solid by-products.
EP-A-289840 has narrated the method for preparing vulcabond through gas phase phosgenation; Gaseous feed reacts in tubular reactor in this invention; Through forming turbulent flow in the tubular space therein; Near tube wall the fluid, in pipe, obtain homogeneous fluid distribution preferably, also therefore obtained narrower time of staying distribution.Also adopted similar blender pattern among the EP-A-570799, in this reactor, owing to do not add measure, mixed and carry out slowly, sufficiently long reactor just can meet the demands.It is the accessory substance that generates polymerization that reactant mixes consequence slowly, and the generation of accessory substance is prone to cause reactor wall coking even blocking channel, thereby shortens the operation cycle of reactor.
US6225497 discloses a kind of micro-structural blender that in the phosgenation reaction process, uses, even the shortcoming of this method is a spot of solid by-product, blender is stopped up.
Summary of the invention
The purpose of this invention is to provide through aromatic diamine; Particularly toluenediamine with gas phase form phosgenation at high temperature, prepares aromatic diisocyanates; The method of TDI particularly; Wherein the reactant incorporation time is shorter than known method, although and can not prevent thoroughly that solid from forming, and can prolong the power lifetime of process units.
Technical scheme of the present invention is following:
The reactor of preparing toluene diisocynate by gaseous phase method of the present invention is tubular reactor 8, in the middle of tubular reactor, is provided with the central-injection device, and taper hydraulic barrier and nozzle are arranged on the central-injection device; The tubular reactor tube wall is provided with hydraulic barrier
Central-injection device 9 of the present invention is fixing through top cover 2; Air current spray nozzle 6 is positioned at the bottom of central-injection device; Central-injection device 9 bottoms are equipped with taper hydraulic barrier 5; Be provided with feed(raw material)inlet 1 above the central-injection device 9, the top of tubular reactor 8 all is provided with feed(raw material)inlet 3, and conical baffled 7 are installed in central-injection device 9 belows.
Central-injection device 9 areas account for 50 ~ 90% of tubular reactor 8 aisle spares.The sectional area ratio of air current spray nozzle 6 total sectional areas and central-injection device 9 is 1: 1～1: 10.
The method of operating of the reactor of preparing toluene diisocynate by gaseous phase method of the present invention; In the inlet 1 and entering tubular reactor 8 of feed stream A through central-injection device 9; Feed stream B gets into the annular space 4 of central-injection device and tubular reactor through tubular reactor 8 inlets 3; Air current A and air-flow B are two reactive materials.
Excessive raw material phosgene mixes with organic amine, and it is 5% ~ 300% that phosgene surpasses amino molal quantity.The raw material organic amine joins in the reactor with gaseous form, and the raw material organic amine is heated to 260～500 ℃; Phosgene is heated to 260～500 ℃ before getting into tubular reactor.
Gaseous reactant of the present invention passes through reactor with the speed of 2～30 meter per seconds, and the time of staying of reactant in reactor is between 0.1 ~ 5 second.
The raw material organic amine is introduced separately or in the presence of the diluent carrier gas.The diluent carrier gas is any diluent gas to reactant and product inertia; Or adopting the steam of solvent for use to dilute the raw material organic amine, selected solvent is any in benzene, xylenes, o-dichlorohenzene or the chlorobenzene.
The present invention provides a kind of reactor and method of operating of preparing toluene diisocynate by gaseous phase method; Wherein adopt reactor of the present invention; Make gas reactant under lower flow velocity, can obtain turbulence-like; And impel the mixing reduced distances of reactant, reduce the generation of solid deposits on the wall of reactor.
Description of drawings
Fig. 1 is the sketch map according to tubular reactor of the present invention.
The specific embodiment
The invention provides the reactor and the method for operating of preparation isocyanates, particularly toluene di-isocyanate(TDI).
As shown in Figure 1; Central-injection device 9 is fixing through top cover 2; Air current spray nozzle 6 is positioned at the bottom of central-injection device, and central-injection device 9 bottoms are equipped with taper hydraulic barrier 5, on central-injection device 9, are provided with feed(raw material)inlet 1; The top of tubular reactor 8 all is provided with feed(raw material)inlet 3, and conical baffled 7 are installed in central-injection device 9 belows.
Feed stream A gets in the tubular reactor 8 through inlet 1 and central-injection device 9.
Central-injection device 9 is fixed on the tubular reactor position through top cover 2, and central-injection device 9 bottoms are equipped with taper hydraulic barrier 5, and air current spray nozzle 6 is positioned at the bottom of central-injection device.
Feed stream B is provided with the annular space 4 that feed(raw material)inlet 3 gets into central-injection device and tubular reactor through the top of tubular reactor 8, is equipped with conical baffled 7 in the pipe reaction with turbulization, strengthens mixed effect.
Method of the present invention can shorten the mixing distance of the material that adds through annular space with through the central-injection device.
Following at reactor embodiment of the present invention: the internal diameter of jet hole 6 is 2～35mm, preferred 3～15mm, and the sectional area ratio of nozzle total sectional area and central-injection device 9 is 1: 1 ~ 1: 10, preferred 1: 2 ~ 1: 5.The centerline direction of nozzle 6 becomes 45 with the centerline direction of central-injection device 9.
In reactor of the present invention, the vertical cross-section drift angle of taper hydraulic barrier 5 is 90 ° of angles, and two base angles are 45.Conical baffled 7 with the tube wall angle of tubular reactor 8 be 45, long-pending 50 ~ 90%, preferred 60 ~ 85% of tubular reactor 8 aisle spares that account for of its center injector face.Conical baffled 7 annular spaces 4 that form with the distance at 9 ends of central-injection device and central-injection device 9 and tubular reactor 8 wide close to well.
In the method for the invention, reactor used length was at least 2.5: 1 with the ratio of diameter, preferably was at least 15: 1.The upper limit of draw ratio depends on the reaction volume that course of reaction is required, in principle not restriction.
Adopt the example of reactor preparing toluene diisocynate by gaseous phase method of the present invention following:
Embodiment 1; The size of the reactor that adopts is: tubular reactor length 0.5m; Central-injection device internal diameter 160mm, outer tube diameter 225mm, central-injection device area accounts for 50% of tubular reactor 8 aisle spares; Jet hole internal diameter 35mm, the sectional area ratio of nozzle total sectional area and central-injection device 9 is 1: 5.
Operating condition: pressure 120kPa, 500 ℃ of temperature, toluenediamine and o-dichlorohenzene that flow is respectively 42.5g/s and 25.5g/s are pre-mixed and are heated to 500 ℃, as air current A, get into reactor through the central-injection device then; Flow is that the phosgene of 103.5g/s is preheated to 500 ℃, as air-flow B, through the annular space entering reactor of tubular reactor.It is 50% that the raw material phosgene surpasses amino molal quantity, and gaseous reactant passes through reactor with the speed of 5 meter per seconds, and the mean residence time of reactant in reactor is 0.1 second.
With the raw material toluenediamine is benchmark, and the yield of toluene di-isocyanate(TDI) is 87%.
Embodiment 2, and the size of the reactor of employing is: tubular reactor length 5m, central-injection device internal diameter 70mm; Outer tube diameter 100mm; Central-injection device area accounts for 50% of tubular reactor 8 aisle spares, jet hole internal diameter 2mm, and the sectional area ratio of nozzle total sectional area and central-injection device 9 is 1: 5.
Operating condition: pressure 120kPa, 260 ℃ of temperature, toluenediamine and o-dichlorohenzene that flow is respectively 17.8g/s and 88.8g/s are pre-mixed and are heated to 260 ℃, as air current A, get into reactor through the central-injection device then; Flow is that the phosgene of 120.7g/s is preheated to 260 ℃, as air-flow B, through the annular space entering reactor of tubular reactor.It is 300% that the raw material phosgene surpasses amino molal quantity, and gaseous reactant passes through reactor with the speed of 10 meter per seconds, and the mean residence time of reactant in reactor is 0.5 second.
With the raw material toluenediamine is benchmark, and the yield of toluene di-isocyanate(TDI) is 92%.
Embodiment 3; The size of the reactor that adopts is: tubular reactor length 10m; Central-injection device internal diameter 160mm, outer tube diameter 200mm, central-injection device area accounts for 64% of tubular reactor 8 aisle spares; Jet hole internal diameter 3mm, the sectional area ratio of nozzle total sectional area and central-injection device 9 is 1: 1.
Operating condition: pressure 120kPa, 260 ℃ of temperature, toluenediamine and o-dichlorohenzene that flow is respectively 37g/s and 97.7g/s are pre-mixed and are heated to 260 ℃, as air current A, get into reactor through the central-injection device then; Flow is that the phosgene of 69.7g/s is preheated to 260 ℃, as air-flow B, through the annular space entering reactor of tubular reactor.It is 5% that the raw material phosgene surpasses amino molal quantity, and gaseous reactant passes through reactor with the speed of 2 meter per seconds, and the time of staying of reactant in reactor is 5 seconds.
With the raw material toluenediamine is benchmark, and the yield of toluene di-isocyanate(TDI) is 88%.
Embodiment 4, and the size of the reactor of employing is: tubular reactor length 3m, central-injection device internal diameter 47mm; Outer tube diameter 50mm; Central-injection device area accounts for 90% of tubular reactor 8 aisle spares, jet hole internal diameter 3mm, and the sectional area ratio of nozzle total sectional area and central-injection device 9 is 1: 10.
Operating condition: pressure 120kPa, 300 ℃ of temperature, toluenediamine and o-dichlorohenzene that flow is respectively 24.4g/s and 122g/s are pre-mixed and are heated to 300 ℃, as air current A, get into reactor through the central-injection device then; Flow is that the phosgene of 43.6g/s is preheated to 300 ℃; As air-flow B, through the annular space entering reactor of tubular reactor, it is 5% that the raw material phosgene surpasses amino molal quantity; Gaseous reactant passes through reactor with the speed of 30 meter per seconds, and the time of staying of reactant in reactor is 0.1 second.
With the raw material toluenediamine is benchmark, and the yield of toluene di-isocyanate(TDI) is 85%.
Embodiment 5; The size of the reactor that adopts is: tubular reactor length 6m; Central-injection device internal diameter 125mm, outer tube diameter 150mm, central-injection device area accounts for 70% of tubular reactor 8 aisle spares; Jet hole internal diameter 8mm, the sectional area ratio of nozzle total sectional area and central-injection device 9 is 1: 5.
Operating condition: pressure 120kPa, 340 ℃ of temperature, toluenediamine and o-dichlorohenzene that flow is respectively 39.3g/s and 354.4g/s are pre-mixed and are heated to 340 ℃, as air current A, get into reactor through the central-injection device then; Flow is that the phosgene of 143g/s is preheated to 340 ℃, as air-flow B, through the annular space entering reactor of tubular reactor.It is 125% that the raw material phosgene surpasses amino molal quantity, and gaseous reactant passes through reactor with the speed of 12 meter per seconds, and the time of staying of reactant in reactor is 0.5 second.
With the raw material toluenediamine is benchmark, and the yield of toluene di-isocyanate(TDI) is 90%.
The reactor of the preparing toluene diisocynate by gaseous phase method that the present invention discloses and discloses and method of operating can be through using for reference this paper disclosure.Although technology of the present invention is described through preferred embodiment; But those skilled in the art obviously can change the techniques described herein in not breaking away from content of the present invention, spirit and scope; More particularly; The replacement that all are similar and change apparent to those skilled in the artly, they are regarded as and are included in spirit of the present invention, scope and the content.
Claims (4)
1. the reactor of preparing toluene diisocynate by gaseous phase method is tubular reactor (8), it is characterized in that being provided with the central-injection device in the middle of the tubular reactor, and taper hydraulic barrier and air current spray nozzle are arranged on the central-injection device; The tubular reactor tube wall is provided with hydraulic barrier; Central-injection device (9) is fixing through top cover (2); Air current spray nozzle (6) is positioned at the bottom of central-injection device; Central-injection device bottom is equipped with taper hydraulic barrier (5); On central-injection device (9), be provided with feed(raw material)inlet (1), the top of tubular reactor (8) is provided with feed(raw material)inlet (3), and conical baffled (7) are installed in central-injection device (9) below.
2. reactor as claimed in claim 1 is characterized in that central-injection device (9) area accounts for 50～90% of tubular reactor (8) aisle spare.
3. reactor as claimed in claim 1 is characterized in that the sectional area ratio of air current spray nozzle (6) total sectional area and central-injection device (9) is 1:1～1:10.
4. utilize the method for the said reactor preparing toluene diisocynate by gaseous phase method of claim 1; It is characterized in that: the feed stream organic amine gets in the tubular reactor (8) through the feed(raw material)inlet (1) of central-injection device (9), and the feed stream phosgene gets into the annular space (4) of central-injection device and tubular reactor through the feed(raw material)inlet (3) of tubular reactor (8); The gentle time gas of air-flow organic amine is two strands of raw materials of reaction; It is 5～300% that the raw material phosgene surpasses molal quantity amino in the organic amine, and the raw material organic amine joins in the reactor with gaseous form, and the raw material organic amine is heated to 260～500 ℃; Phosgene is heated to 260～500 ℃ before getting into tubular reactor.
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| CN2009103065191A CN101670263B (en) | 2009-09-03 | 2009-09-03 | Reactor for preparing toluene diisocynate by gaseous phase method and operation method |
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|---|---|---|---|
| CN2009103065191A CN101670263B (en) | 2009-09-03 | 2009-09-03 | Reactor for preparing toluene diisocynate by gaseous phase method and operation method |
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| CN101670263A CN101670263A (en) | 2010-03-17 |
| CN101670263B true CN101670263B (en) | 2012-11-21 |
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| CN101844064B (en) * | 2010-05-18 | 2014-09-24 | 中国科学院过程工程研究所 | Reactor and method for preparing isocyanate by gas phase pyrolysis |
| CN115253969B (en) * | 2022-07-27 | 2023-08-04 | 宁夏瑞泰科技股份有限公司 | Reactor system for preparing isocyanate and method for preparing isocyanate using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391683A (en) * | 1992-10-16 | 1995-02-21 | Rhone-Poulenc Chimie | Preparation of aromatic polyisocyanates |
| US6225497B1 (en) * | 1998-01-09 | 2001-05-01 | Bayer Aktiengesellschaft | Process for the phosgenation of amines in the gas phase using microstructure mixers |
| CN1304927A (en) * | 2000-12-29 | 2001-07-25 | K·S·T·公司 | Method and apparatus for continuously preparing tolylene diisocyanate |
| CN2444949Y (en) * | 2000-12-29 | 2001-08-29 | K·S·T·公司 | Jet reactor for preparation of toluene vulcabond |
| CN1636972A (en) * | 2003-10-23 | 2005-07-13 | 拜尔材料科学股份公司 | Method for producing isocyanates in the gas phase |
-
2009
- 2009-09-03 CN CN2009103065191A patent/CN101670263B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391683A (en) * | 1992-10-16 | 1995-02-21 | Rhone-Poulenc Chimie | Preparation of aromatic polyisocyanates |
| US6225497B1 (en) * | 1998-01-09 | 2001-05-01 | Bayer Aktiengesellschaft | Process for the phosgenation of amines in the gas phase using microstructure mixers |
| CN1304927A (en) * | 2000-12-29 | 2001-07-25 | K·S·T·公司 | Method and apparatus for continuously preparing tolylene diisocyanate |
| CN2444949Y (en) * | 2000-12-29 | 2001-08-29 | K·S·T·公司 | Jet reactor for preparation of toluene vulcabond |
| CN1636972A (en) * | 2003-10-23 | 2005-07-13 | 拜尔材料科学股份公司 | Method for producing isocyanates in the gas phase |
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| CN101670263A (en) | 2010-03-17 |
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