CN113230984A - Device for producing tertiary amine through continuous reaction of adiabatic fixed bed and production process thereof - Google Patents
Device for producing tertiary amine through continuous reaction of adiabatic fixed bed and production process thereof Download PDFInfo
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- CN113230984A CN113230984A CN202110648109.6A CN202110648109A CN113230984A CN 113230984 A CN113230984 A CN 113230984A CN 202110648109 A CN202110648109 A CN 202110648109A CN 113230984 A CN113230984 A CN 113230984A
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- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- 238000007670 refining Methods 0.000 claims abstract description 12
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- 230000008929 regeneration Effects 0.000 claims abstract description 11
- 238000011069 regeneration method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 25
- 238000007599 discharging Methods 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 11
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 11
- 239000002002 slurry Substances 0.000 description 9
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- -1 mono-long alkyl dimethyl tertiary amine Chemical class 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a device for producing tertiary amine by continuous reaction of an adiabatic fixed bed and a production process thereof, comprising the steps of reacting alcohol with mono (methylamine), di (methylamine), ammonia gas, hydrocyanic acid and the like of reaction raw materials in the adiabatic fixed bed under the working condition of hydrogen to generate tertiary amine and simultaneously generate water and byproducts, carrying out gas-liquid separation on reaction products after heat exchange and cooling, wherein the main component of the separated gas is hydrogen, boosting the hydrogen by a compressor, then circulating the hydrogen back to the adiabatic fixed bed for continuous utilization, removing incompletely reacted raw materials and water from a liquid phase obtained by the reaction through lightness removal, then entering a subsequent refining device, refining to obtain a tertiary amine product, and taking the tertiary amine product as a special condition, the adiabatic fixed bed can also be placed in a rectifying tower, at the moment, the process for producing the tertiary amine by the adiabatic fixed bed reactive rectification process can prolong the regeneration period of a catalyst, the recycle gas may be vented to a small extent to remove carbon oxides and prevent their build up in the reaction system.
Description
Technical Field
The invention relates to the technical field of tertiary amine production through continuous reaction of a heat-insulating fixed bed, in particular to a device for producing tertiary amine through continuous reaction of a heat-insulating fixed bed and a production process thereof.
Background
Tertiary amines are those in which three hydrocarbon groups are attached to the nitrogen in the amine molecule and the nitrogen is a trivalent radical. They can be classified into mono-long alkyl dimethyl tertiary amine, di-long alkyl dimethyl tertiary amine and tri-long alkyl dimethyl tertiary amine according to their structures. The long-chain tertiary amine has wide application range and is very important in the industries of petrochemical industry, agricultural chemicals, medicines and surfactants. Currently, the single long chain alkyl dimethyl tertiary amine accounts for the vast majority of the total tertiary amine production.
The alcohol one-step method is the most important method for producing tertiary amine, the core reaction is that fatty alcohol and methylamine are dehydrogenated or dehydrated to generate tertiary amine under the action of catalyst, and in order to reduce the occurrence of side reaction, the reaction is carried out in the hydrogen environment. The prior tertiary amine device has small scale, so that batch reaction is basically adopted in the world, and the reactors adopted globally at present mainly have two forms, namely a slurry reaction kettle with a coil pipe or a jacket for heat exchange and stirring, and a loop reactor with external circulation heating. The production of domestic tertiary amine is originally from foreign introduction technology, and most of the domestic tertiary amine is produced by adopting a slurry reaction kettle.
The slurry reactor has the advantages of being suitable for batch operation, flexible in product switching, capable of flexibly adjusting product types according to market demands, and capable of producing a plurality of types of tertiary amine products by one production line. But its disadvantages are also very significant:
1) each production line has three or forty devices with complex process flow;
2) the operation steps are more, each batch of reaction needs repeated nitrogen replacement, hydrogen replacement and the like, and the process has higher danger;
3) because of intermittent operation, the heat in the production process can not be reused, and the production cost is high;
4) more hydrogen is discharged in each batch, meanwhile, more byproducts are generated, and the product quality is unstable.
However, the scale of the production line of the tertiary amine device in China is large at present, and some large-scale factories even have more than ten production lines. If the total production capacity of a certain factory in Zhang Home harbor exceeds 5 ten thousand tons/year, more than 10 production lines are possessed. The production lines continuously carry out the processes of nitrogen and hydrogen replacement, pressure rise and emptying, the dangerousness is very obvious, and the production accidents are easy to cause casualties; in addition, the product quality and the production cost are obvious problems.
In view of the problems of the current industrial plants, various new tertiary amine reactors or reaction apparatuses are continuously proposed.
Chinese patent 201310009971.8 proposes a new process for continuously producing tertiary amine by using 3-4 slurry reaction kettles connected in series. Although continuous operation is achieved, the number of reaction kettles is large, the abrasion of the catalyst is serious, and in addition, the separation of the catalyst and materials in each slurry reaction kettle is difficult for long-term operation; resulting in higher investment and operation costs and failure to be put into industrial application.
The process for the batch production of tertiary amines in two-stage slurry reactors in series is disclosed in U.S. Pat. No. 4, 8927772, 2, wherein the aqueous vent gas (mainly hydrogen, entrained moisture, containing CO impurities) from the first reactor is dehydrated to remove CO, and then fed into the second reactor to continue the reaction with alcohol, the reaction product after the reaction is separated, and the hydrogen can be recycled. The improvement of the process is that a reaction kettle is added for removing part of carbon oxides in the circulating hydrogen, thereby improving the performance of the catalyst to a certain extent. But the problems of more complex flow, dangerous device, high cost and environmental protection are not solved. So that it cannot be applied.
Chinese patent CN201320717386.9 proposes a fixed bed continuous tertiary amine production device. The core reactor adopts a tube type fixed bed reactor, the temperature of the reactor is controlled by utilizing a heat exchange medium at the shell side of the reactor, and fresh hydrogen is pumped in by adopting a Venturi. The invention adopts a tubular fixed bed reactor, and produces tertiary amine by a continuous mode, which is a great progress. The process flow is simple, the equipment is less, and the intermittent start-stop replacement and purging can be omitted. The operation cost is also reduced a lot. However, the production of tertiary amine is a hydrogen process, and the tubular fixed bed reactor has many welding seams and is easy to leak, particularly the internal structure is complex and is easy to leak; and the tubular fixed bed reactor has high cost and difficult maintenance. This is why it cannot be generalized.
Disclosure of Invention
The invention aims to provide a device for producing tertiary amine by adiabatic fixed bed continuous reaction and a production process thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a device for producing tertiary amine by a heat insulation fixed bed continuous reaction comprises a tertiary amine production device, wherein a feeding and discharging heat exchanger is arranged on the tertiary amine production device, a fixed bed heat insulation reactor is arranged at one connecting end of the feeding and discharging heat exchanger, a feeding heater is arranged at the other connecting end of the fixed bed heat insulation reactor, the other connecting end of the feeding heater is connected with one connecting end of the feeding and discharging heat exchanger, a first cooler is arranged at the other connecting end of the feeding and discharging heat exchanger, a first separator is arranged at one connecting end of the first cooler, a second cooler is arranged at one connecting end of the first separator, a second separator is arranged at the other connecting end of the second cooler, an amine water pump is arranged at one connecting end of the second separator, a circulating hydrogen compressor is arranged at the other connecting end of the circulating hydrogen compressor, a hydrogen buffer tank is arranged at the other connecting end of the circulating hydrogen buffer tank, and the other connecting end of the hydrogen buffer tank is connected with one connecting end of the feeding and discharging heat exchanger, and the other connecting end of the first separator is provided with a crude tertiary amine pump.
Preferably, the production method of the tertiary amine by the adiabatic fixed bed continuous reaction comprises the following steps: A. reacting a reaction raw material alcohol with reaction raw material amines (mono (methylamine), di (methylamine), ammonia gas, hydrocyanic acid and the like) in a heat-insulating fixed bed under the working condition of hydrogen to generate tertiary amine and generate water and byproducts;
B. after heat exchange and cooling of the reaction product, gas-liquid separation is carried out, and the separated gas is subjected to pressure rise by a compressor and then is circulated back to the heat-insulating fixed bed for continuous utilization;
C. and (3) removing incompletely reacted raw materials and water from the liquid phase obtained by the reaction through light removal, then feeding the liquid phase into a subsequent refining device, and refining to obtain a tertiary amine product.
Preferably, said alcohol according to step a is generally a primary alcohol, having a carbon number from 4 to 40,
the preheated mixture enters a heater to be further heated to the temperature required by the reaction, and the temperature is generally 170-230 ℃.
Preferably, the main component of the gas separated according to the step B is hydrogen, an adiabatic fixed bed reactor is used as a container for amination reaction, the number of adiabatic fixed beds is not more than two, the regeneration of the adiabatic fixed bed catalyst can be carried out in-situ regeneration or ex-situ regeneration,
the fixed bed technology can be combined with rectification to form a process for preparing tertiary amine by reactive rectification.
Preferably, the operation pressure in the adiabatic fixed bed is 0.1-5 Barg, the temperature is 150-280 ℃, and the reactor can be of an upward feeding type or a downward feeding type, and can also enter from the middle part when a plurality of catalyst beds are provided.
Preferably, the feed can be either one or several alcohols.
Preferably, 1-3 catalyst beds are arranged in the reactor, and a cold material distributor can be arranged. Compared with the prior art, the invention has the beneficial effects that:
(1) the adiabatic fixed bed can meet the production requirement, and for the working condition that the amination reaction has more heat release, two adiabatic fixed bed reactors can be arranged, and a cooler is arranged between the two adiabatic fixed bed reactors to control the temperature in the reactors and ensure the activity of the catalyst;
(2) the adiabatic fixed bed reaction process can also be used for a process for preparing tertiary amine by reactive distillation, so that fewer by-products of the prepared crude tertiary amine are generated, and the conversion rate is higher;
(3) the heat exchange of the inlet materials and the outlet material flows of the heat-insulating fixed bed reactor is carried out to fully utilize the waste heat, and the heat exchange forms are various, and can be either shell-and-tube or tube-and-plate;
(4) the process for producing tertiary amine can prolong the regeneration period of the catalyst, and the circulating gas can be discharged with a small amount of air to discharge carbon oxides so as to prevent the carbon oxides from accumulating in a reaction system.
Drawings
FIG. 1 is a schematic view of a tertiary amine production apparatus of the present invention.
FIG. 2 is a schematic view showing the structure of a tertiary amine production apparatus according to the present invention;
FIG. 3 is a schematic view of a tertiary amine production apparatus according to the present invention.
In the figure: 1. a charge and discharge heat exchanger; 2. a feed heater; 3. a fixed bed adiabatic reactor; 4. a first cooler; 5. a first separator; 6. a second cooler; 7. a second separator; 8. a recycle hydrogen compressor; 9. a hydrogen buffer tank; 10. a crude tertiary amine pump; 11. an amine water pump; 12. tertiary amine apparatus for producing.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, the present invention provides a technical solution: a device for producing tertiary amine by a heat insulation fixed bed continuous reaction comprises a tertiary amine production device 12, wherein a feeding and discharging heat exchanger 1 is arranged on the tertiary amine production device 12, a fixed bed heat insulation reactor 3 is arranged at one connecting end of the feeding and discharging heat exchanger 1, a feeding heater 2 is arranged at the other connecting end of the fixed bed heat insulation reactor 3, the other connecting end of the feeding heater 2 is connected with one connecting end of the feeding and discharging heat exchanger 1, a first cooler 4 is arranged at the other connecting end of the feeding and discharging heat exchanger 1, a first separator 5 is arranged at one connecting end of the first cooler 4, a second cooler 6 is arranged at one connecting end of the first separator 5, a second separator 7 is arranged at the other connecting end of the second cooler 6, an amine water pump 11 is arranged at one connecting end of the second separator 7, a circulating hydrogen compressor 8 is arranged at the other connecting end of the circulating hydrogen compressor 8, and a hydrogen buffer tank 9 is arranged at the other connecting end of the circulating hydrogen compressor 8, the other connecting end of the hydrogen buffer tank 9 is connected with one connecting end of the feeding and discharging heat exchanger 1, and the other connecting end of the first separator 5 is provided with a crude tertiary amine pump 10.
An apparatus for producing tertiary amine by adiabatic fixed bed continuous reaction, comprising the steps of:
reacting a reaction raw material alcohol with reaction raw material amines (i.e. mono (methylamine), di (methylamine), ammonia gas, hydrocyanic acid and the like) in a heat insulation fixed bed under the hydrogen condition to generate tertiary amine and water and byproducts, wherein the alcohol for producing the tertiary amine by continuous reaction in the heat insulation fixed bed is generally primary alcohol, the feeding material can be one alcohol or a plurality of alcohols, the carbon number is 4-40, and the preheated mixed material enters a heater to be further heated to the temperature required by the reaction, generally 170-230 ℃.
The method comprises the following steps of carrying out heat exchange and cooling on a reaction product, carrying out gas-liquid separation, wherein the main component of separated gas is hydrogen, taking an adiabatic fixed bed reactor as a container for amination reaction, wherein the number of adiabatic fixed beds is not more than two, 1-3 catalyst bed layers are arranged in the reactor, a cold material distributor can be arranged, the regeneration of the adiabatic fixed bed catalyst can be carried out in the reactor or outside the reactor, the fixed bed technology can be combined with rectification to form a process for preparing tertiary amine by reactive rectification, and the separated gas is recycled to the adiabatic fixed bed for continuous utilization after being boosted by a compressor.
The operation pressure in the adiabatic fixed bed is 0.1-5 Barg, the temperature is 150-280 ℃, and the reactor can be of an upward feeding type or a downward feeding type, and can also enter from the middle part when a plurality of catalyst beds are provided.
And (3) removing incompletely reacted raw materials and water from the liquid phase obtained by the reaction through light removal, then feeding the liquid phase into a subsequent refining device, and refining to obtain a tertiary amine product.
When the tertiary amine is continuously produced by the adiabatic fixed bed, raw material fatty alcohol is firstly mixed with amine (ammonia, hydrocyanic acid and the like) and hydrogen, a mixer can be arranged to increase the mixing effect, the mixture flow is subjected to heat exchange with the discharged material of the reactor, the preheated mixed material enters a heater to be further heated to the temperature required by the reaction, generally 170-230 ℃, and then enters the fixed bed reactor. The fixed bed reactor can be an axial type, 1-3 catalyst bed layers can be arranged in the reactor according to the difference of reaction raw materials, and a cold material distributor can be arranged; according to the difference of raw materials and target products, the upper feeding or the lower feeding of a reactor can be adopted, so that the process flow is optimized, the regeneration period of the catalyst is prolonged, the operating pressure in an adiabatic fixed bed is 0.1-5 Barg, the operating temperature is 150-280 ℃, the space velocity is 0.1-2 hr-, the material flow at the outlet of the reactor exchanges heat with the feeding material, is cooled, enters a first-stage cooler, then enters a first-stage separator to separate out crude tertiary amine, the gas at the top of the first-stage separator enters a second-stage cooler again to be cooled, the cooled material enters the second-stage separator to remove water, unreacted amine (NH3) and the like, the gas at the top of the second-stage separator is mainly hydrogen, is increased by a compressor and then is recycled, a small amount of recycle gas is discharged to discharge carbon oxides to prevent the carbon oxides from accumulating in a reaction system, and the refining equipment is needed after the crude tertiary amine at the bottom of the first-stage separator is removed, and further refining to obtain the tertiary amine product.
When producing tertiary amine, because the raw materials are different, the reaction heat of alcoholysis of some fatty alcohols is high, the raw material fatty alcohols can be mixed with amine (ammonia, hydrocyanic acid, etc.) and hydrogen firstly, a mixer can be arranged to increase the mixing effect, the mixed material flow exchanges heat with the discharged material of the reactor, the preheated mixed material enters a heater to be further heated to the temperature required by the reaction, generally 170-230 ℃, then enters a first fixed bed reactor, the raw materials react in the first reactor to a certain degree, the temperature rise reaches the allowable limit, then the mixed material flows out from the discharge hole of the reactor and enters a cooler, the reaction material is cooled to 170-230 ℃ by the cooler, part of gas is pumped out to an outlet heat exchanger, the rest material flow enters a second reactor to continue amination, the operating pressure in the two adiabatic fixed beds is 0.1-5 Barg, the operating temperature is 150-280 ℃, the outlet material flow of the reactor is cooled after exchanging heat with the fed material, the tertiary amine enters a primary cooler, then the primary separator is used for separating out the crude tertiary amine, the gas at the top of the primary separator enters a secondary cooler again for cooling, the cooled material enters a secondary separator for dehydrating water and unreacted amine (NH3), the gas at the top of the secondary separator is mainly hydrogen, the hydrogen is added by a compressor and then recycled, a small amount of recycle gas is discharged to discharge carbon oxides to prevent the carbon oxides from accumulating in a reaction system, the crude tertiary amine at the bottom of the primary separator is removed by required refining equipment, and a tertiary amine product can be obtained after further refining.
Fixed bed reactors are typically provided with multiple catalyst beds and several packing beds or trays and associated column internals. Raw material aliphatic alcohol is firstly mixed with amine (ammonia, hydrocyanic acid and the like) and hydrogen, a mixer can be arranged to increase the mixing effect, the mixture flow exchanges heat with the discharged material of the reactor, the preheated mixture enters a heater to be further heated to the temperature required by the reaction, generally 170-230 ℃, and then enters the middle part of the fixed bed reactor, a condenser is arranged at an outlet at the upper part of the fixed bed reactor, the temperature of the condenser is controlled, the condensed liquid returns to the top of the fixed bed reactor, the gas phase of the condenser is cooled by a subsequent secondary cooler, the material cooled by the secondary cooler enters a separator, the liquid of the separator mainly comprises water and unreacted amine (ammonia gas and the like), the gas at the outlet of the separator mainly comprises hydrogen, the hydrogen is recycled after the pressurization of a compressor, a little air can be discharged simultaneously to prevent the accumulation of carbon oxides, and a reboiler is arranged at the bottom of the fixed bed reactor, the process route is essentially a process for preparing tertiary amine by reaction rectification, and because a reaction product, namely water, is removed from the top of the tower, the reaction in a catalyst bed layer in the tower can be carried out more quickly and thoroughly. The operating pressure in the adiabatic fixed bed reactor is 0.1-5 Barg, and the operating temperature is 150-300 ℃.
The process for producing tertiary amine by adiabatic fixed bed continuous reaction is carried out by different raw materials
Example 1:
the C12/14 fatty alcohol and dimethylamine are used as raw materials, the whole set of device only needs less than 20 devices, the content of produced tertiary amine is more than 99.5 wt%, the yield is 98.5%, the comprehensive energy consumption is reduced by 70% compared with the slurry reaction kettle process, the economic benefit is very large, the whole set of device is completely automatically controlled, only manual inspection is needed, and the three-waste emission is reduced by 70%.
Example 2:
c12 fatty alcohol and dimethylamine are used as raw materials, and the process route B) in the patent technology is adopted. The whole set of equipment only needs less than 20 devices, the content of the produced tertiary amine is more than 99.7 percent by weight, and the yield is 99.5 percent. The comprehensive energy consumption of the technology is reduced by 75 percent compared with the slurry reaction kettle technology, and the economic benefit is great; the whole device is completely and automatically controlled, only manual inspection is needed, and the three-waste emission is reduced by 75%.
Example 3:
in a certain double long-chain tertiary amine production device, C16 fatty alcohol and monomethylamine are used as raw materials, and a process route C) in the patent technology is adopted. The whole set of equipment only needs less than 25 devices, the content of the produced tertiary amine is more than 99.8 percent by weight, and the yield is 99.2 percent. The comprehensive energy consumption of the technology is reduced by 75 percent compared with the slurry reaction kettle technology, and the economic benefit is great; the whole device is completely and automatically controlled, only manual inspection is needed, and the three-waste emission is reduced by 75%.
The process for producing tertiary amine can prolong the regeneration period of the catalyst, and the circulating gas can be discharged with a small amount of air to discharge carbon oxides so as to prevent the carbon oxides from accumulating in a reaction system.
The three processes for producing tertiary amine are matched with a special catalyst technology, the performance of the catalyst is ensured under the condition that a catalyst bed layer has certain temperature rise, so that the thorough amination reaction is ensured, water and a small amount of byproducts generated by the reaction are continuously brought out of the system, the complete conversion of fatty alcohol is promoted, the impurities of the crude tertiary amine are few, and the crude tertiary amine is further rectified to obtain a tertiary amine product.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. An adiabatic fixed bed continuous reaction apparatus for producing tertiary amine, comprising a tertiary amine production apparatus (12), characterized in that: a feeding and discharging heat exchanger (1) is arranged on the tertiary amine production device (12), a fixed bed adiabatic reactor (3) is arranged at one connecting end of the feeding and discharging heat exchanger (1), a feeding heater (2) is arranged at the other connecting end of the fixed bed adiabatic reactor (3), the other connecting end of the feeding heater (2) is connected with one connecting end of the feeding and discharging heat exchanger (1), a first cooler (4) is arranged at the other connecting end of the feeding and discharging heat exchanger (1), a first separator (5) is arranged at one connecting end of the first cooler (4), a second cooler (6) is arranged at one connecting end of the first separator (5), a second separator (7) is arranged at the other connecting end of the second cooler (6), an amine water pump (11) is arranged at one connecting end of the second separator (7), and a circulating hydrogen compressor (8) is arranged at the other connecting end of the second separator (7), the other connecting end of the circulating hydrogen compressor (8) is provided with a hydrogen buffer tank (9), the other connecting end of the hydrogen buffer tank (9) is connected with one connecting end of the feeding and discharging heat exchanger (1), and the other connecting end of the first separator (5) is provided with a coarse tertiary amine pump (10).
2. An adiabatic fixed bed continuous reaction apparatus for producing tertiary amine, the production method comprises the following steps:
A. reacting a reaction raw material alcohol with reaction raw material amines (mono (methylamine), di (methylamine), ammonia gas, hydrocyanic acid and the like) in a heat-insulating fixed bed under the working condition of hydrogen to generate tertiary amine and generate water and byproducts;
B. after heat exchange and cooling of the reaction product, gas-liquid separation is carried out, and the separated gas is subjected to pressure rise by a compressor and then is circulated back to the heat-insulating fixed bed for continuous utilization;
C. and (3) removing incompletely reacted raw materials and water from the liquid phase obtained by the reaction through light removal, then feeding the liquid phase into a subsequent refining device, and refining to obtain a tertiary amine product.
3. An adiabatic fixed bed continuous reaction apparatus for producing a tertiary amine according to claim 2, wherein: said alcohols according to step a are generally primary alcohols, having a carbon number from 4 to 40,
the preheated mixture enters a heater to be further heated to the temperature required by the reaction, and the temperature is generally 170-230 ℃.
4. The apparatus for producing tertiary amine by adiabatic fixed bed continuous reaction according to claim 1, wherein: the main component of the gas separated according to the step B is hydrogen, the adiabatic fixed bed reactor is used as a container for amination reaction, the number of adiabatic fixed beds is not more than two, the regeneration of the adiabatic fixed bed catalyst can be carried out in-situ regeneration or in-situ regeneration,
the fixed bed technology can be combined with rectification to form a process for preparing tertiary amine by reactive rectification.
5. An adiabatic fixed bed continuous reaction apparatus for producing a tertiary amine according to claim 2 or 3, characterized in that: the operation pressure in the adiabatic fixed bed is 0.1-5 Barg, the temperature is 150-280 ℃, and the reactor can be of an upward feeding type or a downward feeding type, and can also enter from the middle part when a plurality of catalyst beds are provided.
6. An adiabatic fixed bed continuous reaction apparatus for producing a tertiary amine according to claim 2, wherein: the feed may be either one or several alcohols.
7. An adiabatic fixed bed continuous reaction apparatus for producing a tertiary amine according to claim 2, wherein: 1-3 catalyst beds are arranged in the reactor, and a cold material distributor can be arranged.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538205A (en) * | 2008-03-17 | 2009-09-23 | 株洲珊林科技有限公司 | Process system and method for continuously preparing long chain alkyl dimethyl tertiary amine |
| JP2013133328A (en) * | 2011-12-27 | 2013-07-08 | Kao Corp | Method of producing tertiary amine |
| CN203144311U (en) * | 2012-12-30 | 2013-08-21 | 灯塔北方化工有限公司 | Fixed-bed continuous tertiary amine production device |
| CN217120204U (en) * | 2021-06-10 | 2022-08-05 | 天津汇荣化工技术有限公司 | Device for producing tertiary amine through continuous reaction of adiabatic fixed bed |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538205A (en) * | 2008-03-17 | 2009-09-23 | 株洲珊林科技有限公司 | Process system and method for continuously preparing long chain alkyl dimethyl tertiary amine |
| JP2013133328A (en) * | 2011-12-27 | 2013-07-08 | Kao Corp | Method of producing tertiary amine |
| CN203144311U (en) * | 2012-12-30 | 2013-08-21 | 灯塔北方化工有限公司 | Fixed-bed continuous tertiary amine production device |
| CN217120204U (en) * | 2021-06-10 | 2022-08-05 | 天津汇荣化工技术有限公司 | Device for producing tertiary amine through continuous reaction of adiabatic fixed bed |
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