CN109369607B - Device and method for synthesizing trioxymethylene through azeotropic catalytic reaction - Google Patents
Device and method for synthesizing trioxymethylene through azeotropic catalytic reaction Download PDFInfo
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- CN109369607B CN109369607B CN201811358845.2A CN201811358845A CN109369607B CN 109369607 B CN109369607 B CN 109369607B CN 201811358845 A CN201811358845 A CN 201811358845A CN 109369607 B CN109369607 B CN 109369607B
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- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
- C07D323/04—Six-membered rings
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Abstract
The invention discloses a device and a method for synthesizing trioxymethylene by azeotropic catalytic reaction, which comprises a feed pump, a heater, an azeotropic catalytic reaction tower and a finished product rectifying tower which are connected in sequence, wherein raw material formaldehyde aqueous solution and a dehydrating agent firstly enter a tube side of the heater to be heated, then enter the azeotropic catalytic reaction tower to be dehydrated, and the dehydration result is divided into two phases: the gas phase rises to enter the evaporation section and flows out of the tower, and the liquid phase falls into the catalytic section under the action of gravity to carry out polymerization reaction; introducing the polymerization product into a rectifying tower, and fractionating to obtain the product trioxymethylene finished product. After the formaldehyde aqueous solution is mixed with the dehydrating agent, under the synergistic effect of azeotropic dehydration and concentration catalysis, the high-purity trioxymethylene product is produced, the defects and drawbacks of the existing water absorption technology, concentration technology, sulfuric acid catalysis technology and extraction drying technology are overcome, and a new technology with advantages of mild process conditions, short flow, small investment, quick response, high efficiency, low consumption, cleanness and environmental protection is created.
Description
Technical Field
The invention relates to a device and a method for synthesizing trioxymethylene, in particular to a device and a method for synthesizing trioxymethylene by azeotropic catalytic reaction, belonging to the technical field of fine chemical engineering.
Background
Trioxymethylene is an important chemical raw material and has very wide application. The prior art has a mature synthetic technology route: the trioxymethylene is synthesized by using 35-45% formaldehyde aqueous solution as raw material and liquid sulfuric acid as catalyst, thus bringing about the congenital deficiency to the process of synthesizing trioxymethylene: the three wastes are discharged more, the production environment is poor, the flow is long, the investment is large, the corrosion of production equipment is serious, and the like, so the development of a new technology with high efficiency, energy conservation, cleanness and environmental protection is imperative.
The existing synthesis methods are as follows: the preparation method comprises the steps of (1) concentrating formaldehyde aqueous solution with the content of 35-45% under reduced pressure, heating to 100 ℃, entering an enamel reaction kettle, catalyzing with 2-10% sulfuric acid, evaporating and concentrating trioxymethylene aqueous solution, extracting and refining again, and drying to obtain a final finished product. The technology is a new technology for synthesizing trioxymethylene by using an azeotropic catalysis tubular bed reactor, directly using formaldehyde aqueous solution to integrate azeotropic dehydration and catalysis, and simultaneously generating dehydration and catalysis synergistic effect under the action of a dehydrating agent.
Disclosure of Invention
Aiming at the inherent shortages of the catalytic synthesis of trioxymethylene by the sulfuric acid method in the prior art, the invention provides a device and a method for azeotropic catalytic synthesis of trioxymethylene, which overcome the defects and drawbacks of the existing water absorption technology, concentration technology, sulfuric acid catalytic technology, extraction drying technology and the like, and create a method and a device with mild process conditions, short process flow, small investment, quick response, high efficiency, low consumption, cleanness and environmental protection.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the device for synthesizing trioxymethylene by azeotropic catalytic reaction comprises a feeding pump, a heater, an azeotropic catalytic reaction tower and a finished product rectifying tower which are sequentially connected, wherein raw material formaldehyde aqueous solution and a dehydrating agent firstly enter a tube side of the heater to be heated, then enter the azeotropic catalytic reaction tower to be dehydrated, and the dehydration result is divided into two phases: the gas phase rises to enter the azeotropic dehydration section and flows out of the tower, and the liquid phase falls into the catalytic section under the action of gravity to carry out polymerization reaction; introducing the polymerization product into a rectifying tower, and fractionating to obtain a product trioxymethylene finished product; the method is characterized in that:
the feed pump is provided with an inlet 7A and an outlet 7B, wherein: the inlet 7A is connected with a device capable of providing raw formaldehyde aqueous solution and a dehydrating agent;
the heater is provided with an inlet 6A and an outlet 6B, wherein: the inlet 6A is connected with the outlet 7B of the feed pump;
the azeotropic catalytic reaction tower is characterized in that a gas phase outlet 1A is formed in the top of the azeotropic catalytic reaction tower, a discharge hole 1E is formed in the bottom of the azeotropic catalytic reaction tower, a first backflow liquid inlet 1B is formed in the upper part of the side wall of the azeotropic catalytic reaction tower, a feed inlet 1C is formed in the middle of the azeotropic catalytic reaction tower, a heating liquid outlet 1F and a heating liquid inlet 1D are formed in the middle of the azeotropic catalytic reaction tower, a second backflow liquid inlet 1G is formed in the lower part of the azeotropic catalytic reaction tower, and the position of the heating liquid inlet 1D is lower than that of the heating liquid outlet 1F; wherein: the feed inlet 1C is connected with an outlet 6B of the heater; the gas phase outlet 1A is sequentially connected with a condenser I, a reflux tank I and a reflux pump I, and the pump outlet of the reflux pump I is connected with a first reflux liquid inlet 1B; the heating liquid inlet 1D is connected with a hot water pump, and the heating liquid outlet 1F is connected with a hot water collecting system;
the finished product rectifying column, the top be equipped with gaseous phase export 8C, the bottom is equipped with finished product discharge gate 8D, the lateral wall top is equipped with the return port 8B, the middle part is equipped with feed inlet 8A, wherein: the feed inlet 8A is connected with the discharge outlet 1E of the azeotropic catalytic reaction tower; the gas phase outlet 8C is sequentially connected with a condenser II, a reflux tank II and a reflux pump II; the outlet of the reflux pump is divided into three paths, one path is connected with the reflux outlet 8B, the other path is connected with the first reflux inlet 1B of the azeotropic catalytic tower, and the third path is connected with the second reflux inlet 1G of the azeotropic catalytic tower, and continuously enters the azeotropic catalytic tower for continuous dehydration and recycling; the discharge hole 8D is connected with a device for collecting or receiving finished trioxymethylene.
In the technical scheme, the azeotropic catalytic reaction tower is provided with a demister at the inner top end, wherein the lower part of the demister comprises an azeotropic dehydration section positioned at the upper part and a catalytic section positioned at the lower part, and the top of the azeotropic dehydration section is sequentially provided with a distributor and a grating plate from top to bottom; the top of the catalytic section is provided with a distributor and a grating plate in sequence from top to bottom, and the bottom of the catalytic section is provided with the distributor, a cushion layer and the grating plate in sequence from top to bottom; the azeotropic dehydration section is provided with tower internals, and the tower internals comprise any one of structured packing or tower plates; the tower internals are selected to comprise structured packing, the number of the structured packing filling sections is N, and N is less than or equal to 1 and less than or equal to 100, the height of each section is 1-3 m, a distributor and a grating plate are arranged between each section, and the distributor is arranged on the grating plate; or the tower internals comprise tower plates, wherein the number of the tower plates is M, and M is less than or equal to 1 and less than or equal to 100; the catalytic section comprises a tubular bed, the number of the catalytic section is N, N is more than or equal to 1 and less than or equal to 10, and a distributor, a cushion layer and a grating plate are sequentially arranged between the sections from top to bottom;
the tube nest comprises a plurality of vertically arranged tube nest, a module catalyst is filled in the tube nest, a heating liquid flow channel is arranged between the outer wall of the tube nest and the inner wall of the reaction tower, the top and the bottom of the tube nest are respectively provided with a closed baffle plate for closing the upper end and the lower end of the heating liquid flow channel, and a plurality of openings are arranged on the baffle plates and communicated with the two openings of the corresponding tube nest; the reaction raw materials flowing down from the azeotropic dehydration section sequentially pass through each distributor, the cushion layer, the grating plate and the tube array in the multi-section catalytic section to be discharged;
the top of the azeotropic catalytic reaction tower is provided with a gas phase outlet 1A, the bottom of the azeotropic catalytic reaction tower is provided with a discharge port 1E, the side wall of the azeotropic catalytic reaction tower is provided with a heating liquid inlet 1D at the bottom of the tubular bed, the opposite side of the heating liquid inlet 1D is provided with a heating liquid outlet 1F at the top of the tubular bed on the side wall of the azeotropic catalytic reaction tower, a distributor at the uppermost part of the azeotropic catalytic reaction tower is communicated with a first backflow liquid inlet 1B arranged on the side wall of the azeotropic catalytic reaction tower, a distributor at the lowermost part of the azeotropic catalytic reaction tower is communicated with a second backflow liquid inlet 1G arranged on the side wall of the azeotropic catalytic reaction tower, and a distributor above the tower internals is communicated with a feed inlet 1C arranged on the side wall of the azeotropic catalytic reaction tower.
In the technical scheme, the cushion layer is a five-layer layered structure formed by combining quartz sand or porcelain balls with different granularity, and the five-layer layered structure is five-level grading: the granularity of the uppermost layer is close to or slightly larger than that of the catalyst, the granularity of the lowermost layer is slightly larger than the gap dimension of the grating plate, three layers are arranged in a mode of gradually increasing from top to bottom and the upper and lower granularity is connected, and the thickness of each layer is 5-15 cm.
In the technical scheme, the demister, the distributor and the grating plate are all made of stainless steel.
In the above technical scheme, each section is provided with a heating liquid inlet 1D and a heating liquid outlet 1F on the catalytic section.
In the above technical solution, the structure of the module catalyst is the same as that of the module catalyst in patent 201620189729.2: the catalyst comprises a catalyst, a wire mesh and a wire mesh corrugated plate, wherein the module catalyst is formed by arranging the wire mesh and the wire mesh corrugated plate in parallel at intervals, catalyst particles are held between two wire meshes to form a catalyst layer, and the catalyst particles in the catalyst layer are arranged by the wire mesh corrugated plate at intervals; the catalyst layers in the module catalyst are arranged at intervals.
In the technical scheme, the catalyst in the module catalyst is a strong acid resin catalyst, a high temperature resistant strong acid resin catalyst and a metal-loaded super acid resin catalyst; preferably a spherical or beaded strong acid resin catalyst, a high temperature resistant strong acid resin catalyst or a metal supported super acid resin catalyst; the type of the load metal is main group II and VIII elements of the periodic table, and the load is 1-20% of the exchange amount of the resin catalyst.
In the technical scheme, the number of the tubes in each section is F, and F is less than or equal to 1 and less than or equal to 10x10 4 The method comprises the steps of carrying out a first treatment on the surface of the Each pipe diameter is E, and E is more than or equal to 2 and less than or equal to 30cm.
In the above technical scheme, the dehydrating agent added into the azeotropic catalytic reaction tower from the feed pump is any one of dichloroethane, benzene, aromatic hydrocarbon and cyclohexane, or a mixture of two or more of them in any proportion.
In the technical scheme, the reflux tank I is provided with a liquid inlet, a liquid outlet and a water outlet, and a coalescer is arranged in the reflux tank I; the liquid inlet is connected with the outlet of the condenser I, the liquid outlet is connected with the pump inlet of the reflux pump I, the water outlet is connected with the wastewater treatment system, the gas phase is condensed by the condenser I to form a liquid phase, and the liquid phase enters the reflux tank I and then the dehydrated water is discharged from the water outlet under the double functions of the coalescer and the static layering.
In the technical scheme, a reboiler is arranged below the side wall of the finished product rectifying tower.
In the invention, the condenser I, the reflux tank I, the coalescer, the reflux pump I, the heater, the feed pump, the finished product rectifying tower, the reboiler, the condenser II, the reflux tank II and the reflux pump II are all commercial products in the field or conventional products with corresponding functions.
The invention also provides a method for synthesizing trioxymethylene by azeotropic catalytic reaction, the flow chart is shown in figure 1, and the method comprises the following steps:
(1) Azeotropic dehydration: heating formaldehyde aqueous solution and dehydrating agent to 50-100 ℃ and then reaching azeotropic temperature, and leading out water by changing water and part of dehydrating agent into gas phase so as to achieve the purpose of concentrating formaldehyde, wherein the mixture formed after dehydration is concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent; the vapor phase water and partial dehydrating agent are condensed and coalesced to form liquid phase water and liquid phase dehydrating agent, the liquid phase water is discharged, and the liquid phase dehydrating agent is recycled;
(2) Polymerization reaction: the mixture formed in the step (1) is polymerized under the catalysis of the catalyst A to generate trioxymethylene aqueous solution, and after the polymerization, the product is the trioxymethylene aqueous solution and a small amount of unvaporized dehydrating agent;
(3) And (3) product fractionation: fractionating the product formed in step (2) under heating to obtain a gas phase and a liquid phase; the gas phase is the dehydrating agent and a small amount of water existing in the product, a part of the dehydrating agent and a part of the water are returned to the step (1) for recycling after condensation, and the liquid phase is the finished product of trioxymethylene and is recovered.
In the technical scheme, the method specifically comprises the following steps:
(1) Azeotropic dehydration: the formaldehyde aqueous solution and the dehydrating agent are introduced into a tube side of a heater by a feed pump to be heated, the temperature reaches the azeotropic temperature after being heated to 50-100 ℃ under the condition of normal pressure or micro-positive pressure, and the formaldehyde aqueous solution and the dehydrating agent are introduced into an azeotropic dehydration section of an azeotropic catalytic reaction tower by a feed port 1C to be subjected to azeotropic dehydration, so that the purpose of concentrating formaldehyde is achieved, and two phases are formed in the tower under the action of an azeotropic principle: the gas phase is water and partial dehydrating agent, and the liquid phase is dehydrated and concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent; wherein: the gas phase rises to the top of the tower and is discharged from a gas phase outlet 1A, and the gas phase is condensed by a condenser I to form liquid phase water and a dehydrating agent, the liquid phase water and the dehydrating agent discharge the dehydrated water through a water outlet under the double functions of a coalescer in a reflux tank I and static layering, and the liquid phase dehydrating agent is pumped to a first reflux port 1B by a reflux pump I so as to be totally refluxed to an azeotropic catalytic reaction tower for recycling; the dehydrated and concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent can downwards flow into the catalytic section of the azeotropic catalytic reaction tower under the action of gravity;
(2) Polymerization reaction: the dehydrated and concentrated formaldehyde aqueous solution descends to a tubular bed of a catalytic section, and is polymerized under the catalysis of a catalyst in the tubular to generate trioxymethylene aqueous solution, and after the polymerization, the product is the trioxymethylene aqueous solution and a small amount of unvaporized dehydrating agent; the product continuously descends to the bottom of the tower under the action of gravity, is discharged from a discharge port 1E and is led into a finished product rectifying tower from a feed port 8A; the heating liquid inlet 1D of the catalytic section is connected with a hot water pump, hot water provided by the hot water pump enters the shell side of the catalytic section to provide temperature for polymerization reaction in the tube array, and the heating liquid outlet 1F is connected with a hot water collecting system;
(3) And (3) product fractionation: after the product formed in the step (2) is led into a finished rectifying tower, fractional distillation is carried out under the heating state of a reboiler, so as to obtain a gas phase and a liquid phase; the gas phase is a dehydrating agent and a small amount of water existing in the product, the dehydrating agent and the small amount of water are discharged from a gas phase outlet 8C and enter a condenser II for condensation, the dehydrating agent and the small amount of water obtained by condensation sequentially flow through a reflux tank II and a reflux pump II and are divided into three paths, one path is connected with a reflux port 8B, the other path is connected with a first reflux liquid inlet 1B of an azeotropic catalytic tower, and the third path is connected with a second reflux liquid inlet 1G communicated with the lowest part of a tubular bed, and continuously enters a tubular bed for continuous dehydration and recycling; the liquid phase obtained at the bottom of the tower is the pure trioxymethylene product, which is discharged and collected by a discharge hole 8D.
In the technical scheme, in the step (1), the proportion of the dehydrating agent to the formaldehyde aqueous solution is determined according to azeotropic composition and formaldehyde concentration, and the mass ratio can be mastered in the range of 1-10:1, a step of; namely, the mass ratio of the dehydrating agent to formaldehyde in the formaldehyde aqueous solution is 1-10:1, a step of; the mass fraction of formaldehyde in the formaldehyde aqueous solution is 30-55%.
In the above technical scheme, in the step (1), the dehydrating agent is any one of pure benzene, aromatic hydrocarbon, dichloroethane and cyclohexane, or a mixture of two or more of them mixed in any proportion.
In the above technical scheme, in the step (2), the catalyst is a strong acid resin catalyst, a high temperature resistant strong acid resin catalyst, and a metal-loaded super acid resin catalyst; preferably a spherical or beaded strong acid resin catalyst, a high temperature resistant strong acid resin catalyst or a metal supported super acid resin catalyst; the type of the load metal is main group II and VIII elements of the periodic table, and the load is 1-20% of the exchange amount of the resin catalyst.
In the above technical scheme, in the step (2), the temperature of the hot water provided by the hot water pump is 80-120 ℃, so that the temperature of the polymerization reaction in the tube nest is ensured to be 70-110 ℃.
In the above technical scheme, in the step (3), the operation conditions of the finished product rectifying tower are as follows: overhead temperature: 30-110 ℃; bottom temperature: 80-180 ℃; operating pressure: 0.01-1.5Mpa.
In the technical scheme, in the step (3), the dehydrating agent obtained by condensation and a small amount of water flow back to the finished product rectifying tower from the reflux port 8B, and the reflux ratio is 0.1-2.0.
The technical scheme of the invention has the advantages that: the method replaces the connection of a plurality of distributed components in the existing equipment, integrates a plurality of functions into one reaction tower, greatly simplifies the production process, shortens the reaction time, and has obvious effect in efficiently preparing the trioxymethylene. After the formaldehyde aqueous solution is mixed with the entrainer, under the synergistic effect of azeotropic dehydration and concentration catalysis, the high-purity trioxymethylene product is produced, and the existing problems are overcome: the water absorption technology, the concentration technology, the sulfuric acid catalysis technology and the extraction drying technology have the defects and drawbacks, so that a process is mild in condition, short in process flow, small in investment and quick in effect; high efficiency, low consumption, cleanness and environmental protection, and has a plurality of advantages.
Drawings
Fig. 1 is: the invention relates to a flow chart of a method for synthesizing trioxymethylene by azeotropic catalysis;
fig. 2 is: the structure diagram of the device for synthesizing trioxymethylene by azeotropic catalysis in the invention;
fig. 3 is: schematic diagram of the internal structure of the azeotropic catalytic reaction tower;
fig. 4 is: schematic structural diagram of the modular catalyst at the cross section of a single tube array;
wherein: 1-azeotropic catalytic reaction tower, 101-gas phase outlet 1A, 102-first reflux liquid inlet 1B, 103-feed inlet 1C, 104-heating liquid inlet 1D, 105-discharge outlet 1E, 106-heating liquid outlet 1F, 107-second reflux liquid inlet 1G, 2-condenser I, 3-reflux tank I, 4-coalescer, 5-reflux pump I, 6-heater, 7-feed pump, 8-finished product rectifying tower, 9-reboiler, 10-condenser II, 11-reflux tank II, 12-reflux pump II; 13-demister, 14-distributor, 15-tower internals, 16-column bed, 17-column, 18-bedding, 19-grid plate, 40-module catalyst, 401-catalyst layer, 402-wire mesh, 403-wire mesh corrugated plate.
Detailed Description
The following detailed description of the technical scheme of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention firstly provides a device for synthesizing trioxymethylene by azeotropic catalytic reaction, which comprises a feed pump 7, a heater 6, an azeotropic catalytic reaction tower 1 and a finished product rectifying tower 8 which are sequentially connected, wherein raw material formaldehyde aqueous solution and a dehydrating agent firstly enter a tube side of the heater 6 to be heated, then enter the azeotropic catalytic reaction tower to be dehydrated, and the dehydration result is divided into two phases: the gas phase rises to enter the azeotropic dehydration section and flows out of the tower, and the liquid phase falls into the catalytic section under the action of gravity to carry out polymerization reaction; introducing the polymerization product into a rectifying tower 8, and fractionating to obtain a product trioxymethylene finished product; as shown in fig. 2-4:
the feed pump 7 is provided with an inlet 7A and an outlet 7B, wherein: the inlet 7A is connected with a device capable of providing raw formaldehyde aqueous solution and a dehydrating agent;
the heater 6 is provided with an inlet 6A and an outlet 6B, wherein: the inlet 6A is connected with the outlet 7B of the feed pump;
the azeotropic catalytic reaction tower 1 is characterized in that a gas phase outlet 1A 101 is formed in the top of the azeotropic catalytic reaction tower, a discharge hole 1E 105 is formed in the bottom of the azeotropic catalytic reaction tower, a first reflux inlet 1B 102 is formed in the upper part of the side wall of the azeotropic catalytic reaction tower, a feed inlet 1C 103 is formed in the middle of the azeotropic catalytic reaction tower, a heating liquid outlet 1F 106 and a heating liquid inlet 1D 104 are formed in the middle of the azeotropic catalytic reaction tower, a second reflux inlet 1G 107 is formed in the lower part of the azeotropic catalytic reaction tower, and the position of the heating liquid inlet 1D is lower than that of the heating liquid outlet 1F; wherein: the feed inlet 1C is connected with an outlet 6B of the heater 6; the gas phase outlet 1A is sequentially connected with a condenser I2, a reflux tank I3 and a reflux pump I5, and the pump outlet of the reflux pump I is connected with a first reflux liquid inlet 1B; the heating liquid inlet 1D is connected with a hot water pump, and the heating liquid outlet 1F is connected with a hot water collecting system;
the finished product rectifying column 8, the top be equipped with gaseous phase export 8C, the bottom is equipped with finished product discharge gate 8D, the lateral wall top is equipped with the return port 8B, the middle part is equipped with feed inlet 8A, wherein: the feed inlet 8A is connected with the discharge outlet 1E of the azeotropic catalytic reaction tower; the gas phase outlet 8C is sequentially connected with a condenser II 10, a reflux tank II 11 and a reflux pump II 12; the pump outlet of the reflux pump 12 is divided into three paths, one path is connected with the reflux port 8B, the other path is connected with the first reflux inlet 1B of the azeotropic catalytic tower, and the third path is connected with the second reflux inlet 1G of the azeotropic catalytic tower, and continuously enters the azeotropic catalytic tower for continuous dehydration and recycling; the discharge hole 8D is connected with a device for collecting or receiving finished trioxymethylene.
The top of the azeotropic catalytic reaction tower 1 is provided with a demister 13, the lower part of the demister 13 comprises an azeotropic dehydration section positioned at the upper part and a catalytic section positioned at the lower part, and the top of the azeotropic dehydration section is sequentially provided with a distributor 14 and a grating plate 19 from top to bottom; the top of the catalytic section is provided with a distributor 14 and a grating plate 19 in sequence from top to bottom, and the bottom of the catalytic section is provided with the distributor 14, a cushion layer 18 and the grating plate 19 in sequence from top to bottom; the azeotropic dehydration section is provided with a tower internal part 15, and the tower internal part 15 comprises any one of structured packing or tower plates; the tower internal part 15 is selected to comprise structured packing, the number of the structured packing filling sections is N, and N is less than or equal to 1 and less than or equal to 100, the height of each section is 1-3 meters, a distributor 14 and a grating plate 19 are arranged between each section, and the distributor 14 is arranged above the grating plate 19; or the tower inner part 15 is selected from a tower plate, wherein the number of the tower plates is M, and M is more than or equal to 1 and less than or equal to 100; the catalytic section comprises a tubular bed 16, the number of the catalytic section is N, N is more than or equal to 1 and less than or equal to 10, and a distributor 14, a cushion layer 18 and a grid plate 19 are sequentially arranged between the sections from top to bottom;
the tube nest 16 comprises a plurality of vertically arranged tube nest 17, a module catalyst 40 is filled in the tube nest 17, a heating liquid flow channel is arranged between the outer wall of the tube nest 17 and the inner wall of the reaction tower 1, the top and the bottom of the tube nest 16 are respectively provided with a closed baffle plate for closing the upper end and the lower end of the heating liquid channel, and a plurality of openings are arranged on the baffle plates and communicated with the two openings of the corresponding tube nest 17; the reaction raw materials flowing down from the azeotropic dehydration section pass through each distributor 14, the cushion layer 18, the grating plate 19 and the tube array 17 in the multi-section catalytic section in sequence to be discharged;
the top of the reaction tower 1 is provided with a gas phase outlet 1A 101, the bottom of the reaction tower 1 is provided with a discharge outlet 1E 105, the side wall of the reaction tower 1 is provided with a heating liquid inlet 1D 104 positioned at the bottom of the column bed 16, the opposite side of the heating liquid inlet 1D 104 is provided with a heating liquid outlet 1F 106 positioned at the top of the column bed 16 on the side wall of the reaction tower 1, a distributor 14 at the uppermost part of the reaction tower 1 is communicated with a first backflow liquid inlet 1B 102 arranged on the side wall of the reaction tower 1, a distributor 14 at the lowermost part of the reaction tower 1 is communicated with a second backflow liquid inlet 1G 107 arranged on the side wall of the reaction tower, and a distributor 14 above a tower internal 15 in the middle part is communicated with a feed inlet 1C 103 arranged on the side wall of the reaction tower 1;
the cushion layer 18 is a five-layer laminated structure formed by combining quartz sand or porcelain balls with different granularity, and the five-layer laminated structure is five-level grading: the granularity of the uppermost layer is close to or slightly larger than that of the catalyst, the granularity of the lowermost layer is slightly larger than the gap dimension of the grating plate 19, three layers are arranged in a mode of gradually increasing from top to bottom and the upper and lower granularity is connected, and the thickness of each layer is 5-15 cm; the function of which is to allow the liquid phase fluid to pass through, while the catalyst in the interception tube 17 is exposed; the grating plates 19 function as support mats 18;
the foam remover 13, the distributor 14 and the grating plate 19 are all made of stainless steel;
a heating liquid inlet 1D 104 and a heating liquid outlet 1F 106 are arranged on each catalytic section;
the modular catalyst 40 has the same structure as the modular catalyst of patent 201620189729.2: the catalyst module comprises a catalyst, a wire mesh 402 and a wire mesh corrugated plate 403, wherein the module catalyst 40 is formed by arranging the wire mesh 402 and the wire mesh corrugated plate 403 in parallel at intervals, the catalyst particles are held between two wire mesh 402 to form a catalyst layer 401, and the catalyst particles in the catalyst layer 401 are separated by the wire mesh corrugated plate 403; the catalyst layers 401 in the module catalyst 40 are arranged at intervals;
the catalyst in the module catalyst 40 is a strong acid resin catalyst, a high temperature resistant strong acid resin catalyst, and a metal-loaded super acid resin catalyst; preferably a spherical or beaded strong acid resin catalyst, a high temperature resistant strong acid resin catalyst or a metal supported super acid resin catalyst; the type of the load metal is main group II and VIII elements of the periodic table, and the load is 1-20% of the exchange amount of the resin catalyst;
the dehydrating agent added into the azeotropic catalytic reaction tower from the feed pump is any one of dichloroethane, benzene, aromatic hydrocarbon and cyclohexane or a mixture formed by mixing two or more of them according to any proportion;
if the tower internal part 15 in the azeotropic catalytic reaction tower is structured packing, the packing section number is N, N is less than or equal to 1 and less than or equal to 100, and the height of each section is 1-3 m; a distributor 14 and a grating plate 19 are arranged between each two sections; if the column plates are the column plates, the theoretical plate number is M, and M is less than or equal to 1 and less than or equal to 100, and the foam remover 13 is arranged at the top end of the column;
the catalytic section of the azeotropic catalytic reaction tower is a tubular bed section, and the number of the catalytic section is N, and N is more than or equal to 1 and less than or equal to 10; a distributor 14, a cushion layer 18 and a grating plate 19 are arranged between each two sections;
the number of 17 tubes of each section of tube array is F, and F is more than or equal to 1 and less than or equal to 10x10 4 The method comprises the steps of carrying out a first treatment on the surface of the Each pipe diameter is E, and E is more than or equal to 2 and less than or equal to 30cm.
The reflux tank I3 is provided with a liquid inlet, a liquid outlet and a water outlet, and a coalescer 4 is arranged in the reflux tank I; the liquid inlet is connected with the outlet of the condenser I2, the liquid outlet is connected with the pump inlet of the reflux pump I5, the water outlet is connected with the wastewater treatment system, the gas phase is condensed by the condenser I to form a liquid phase, and the liquid phase enters the reflux tank I and then the dehydrated water is discharged from the water outlet under the double functions of the coalescer and the static layering.
And a reboiler 9 is arranged below the side wall of the finished product rectifying tower 8.
In the invention, the condenser I, the reflux tank I, the coalescer, the reflux pump I, the heater, the feed pump, the finished product rectifying tower, the reboiler, the condenser II, the reflux tank II and the reflux pump II are all commercial products in the field or conventional products with corresponding functions.
The invention also provides a method for synthesizing trioxymethylene by azeotropic catalytic reaction, which comprises the following steps:
(1) Azeotropic dehydration: heating formaldehyde aqueous solution and dehydrating agent to 50-100 ℃ and then reaching azeotropic temperature, and leading out water by changing water and part of dehydrating agent into gas phase so as to achieve the purpose of concentrating formaldehyde, wherein the mixture formed after dehydration is concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent; the vapor phase water and partial dehydrating agent are condensed and coalesced to form liquid phase water and liquid phase dehydrating agent, the liquid phase water is discharged, and the liquid phase dehydrating agent is recycled;
(2) Polymerization reaction: the mixture formed in the step (1) is polymerized under the catalysis of the catalyst A to generate trioxymethylene aqueous solution, and after the polymerization, the product is the trioxymethylene aqueous solution and a small amount of unvaporized dehydrating agent;
(3) And (3) product fractionation: fractionating the product formed in step (2) under heating to obtain a gas phase and a liquid phase; the gas phase is the dehydrating agent and a small amount of water existing in the product, a part of the dehydrating agent and a part of the water are returned to the step (1) for recycling after condensation, and the liquid phase is the finished product of trioxymethylene and is recovered.
The invention is illustrated below in connection with specific examples:
example 1:
a method for synthesizing trioxymethylene by azeotropic catalytic reaction comprises the following steps:
(1) Azeotropic dehydration: firstly, introducing 100g of 50% formaldehyde aqueous solution and 80g of dichloroethane (dehydrating agent) into a heater 6 by a feed pump 7, heating to 70-75 ℃ under normal pressure, then, entering an azeotropic dehydration section in an azeotropic catalytic reaction tower 1 from a feed port 1C, wherein the temperature is just the azeotropic temperature of the dichloroethane and water, so that water with azeotropic components is gasified and rises to a gas phase outlet 1A, namely 10% of water and 50g of dichloroethane, and sequentially passes through a condenser I2, a reflux tank I3 and a reflux pump I5, wherein about 50g of dichloroethane is returned to the azeotropic catalytic reaction tower 1 by a first reflux inlet 1B for recycling, and the water in the reflux tank I is separated under the action of a coalescer 4 and is discharged to a sewage treatment system from a water outlet at the bottom of the reflux tank I; the remaining 30g of unvaporised dichloroethane continue down with the aqueous formaldehyde solution enriched to 60% to the column bed.
(2) Polymerization reaction: carrying out polymerization reaction on formaldehyde aqueous solution with the concentration of 60% under the catalysis of a resin catalyst in a tube array, and the hot water temperature of a tube array bed in an azeotropic catalytic reaction tower at 98-100 ℃ and under normal pressure to obtain 80g of polymerization mixed product, wherein 50g of the polymerization mixed product is trioxymethylene (approximately containing about 2g of water), and 30g of the polymerization mixed product is dichloroethane; the polymerization mixture gradually falls into the bottom of the column, is discharged from the discharge port 1E and is continuously introduced into the final rectifying column 8 from the feed port 8A.
(3) And (3) product fractionation: under the heating condition of a reboiler 9, about 32G of dichloroethane and water are evaporated to a gas phase outlet 8C, the gas phase outlet is divided into three paths after passing through a condenser II 10, a reflux tank II 11 and a reflux pump II 12 in sequence, one path of the gas phase outlet flows back to a finished product rectifying tower from a reflux inlet 8B by 6.4G (reflux ratio is 0.2), the other path of the gas phase outlet 20G of dichloroethane returns to a tubular bed from a second reflux inlet 1G for recycling, and the other path of the gas phase outlet 5.6G of dichloroethane returns to an azeotropic dehydration section from a first reflux inlet 1B for recycling, so that 48G of trioxymethylene is obtained at the bottom of the tower; the operating conditions of the finished product rectifying tower are as follows: the temperature of the tower top is 70-90 ℃, 0.1MPa, the temperature of the tower bottom is 80-120 ℃ and 0.15MPa.
In this example, the yield of the final product was 95% or more and the purity was nearly 100%.
In the embodiment, the resin catalyst contained in the tube array is a module catalyst with an active component of D006;
in this example, the azeotropic catalytic reaction tower 1 is designed as follows: the column bed is divided into two sections, each section is 1m in height, 3 column pipes 17 are arranged in each section, the diameter of each column pipe is 5cm, and a distributor 14, a cushion layer 18 and a grid plate 19 are arranged between each section from top to bottom. The azeotropic dehydration section is structured packing, and is two sections, and every section height is 1m, and every section is equipped with distributor 14 from top to bottom, grid board 19, and tower top exit is equipped with demister 13. The foam remover, the distributor and the structured packing are all made of stainless steel;
in this embodiment, the pad layer is made of porcelain balls.
Example 2:
a method for synthesizing trioxymethylene by azeotropic catalysis is the same as that of example 1, except that the feeding amount of formaldehyde aqueous solution and dichloroethane is increased by 1 time, the column bed 16 is set to be one section, each section is 1m high, 3 column pipes 17 are arranged in each section, and the diameter of each column pipe 17 is 5cm. The yield of the finished product is still kept at about 95 percent and the purity is nearly 100 percent.
The foregoing examples are merely illustrative of the technical concept and technical features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the essence of the present invention should be included in the scope of the present invention.
Claims (10)
1. The method for synthesizing the trioxymethylene by azeotropic catalytic reaction is characterized by comprising the following steps of:
(1) Azeotropic dehydration: heating formaldehyde aqueous solution and dehydrating agent to 50-100 ℃ and then reaching azeotropic temperature, and leading out water by changing water and part of dehydrating agent into gas phase so as to achieve the purpose of concentrating formaldehyde, wherein the mixture formed after dehydration is concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent; the vapor phase water and partial dehydrating agent are condensed and coalesced to form liquid phase water and liquid phase dehydrating agent, the liquid phase water is discharged, and the liquid phase dehydrating agent is recycled; the dehydrating agent is any one of pure benzene, dichloroethane and cyclohexane, or a mixture formed by mixing two or more of the pure benzene, the dichloroethane and the cyclohexane according to any proportion;
(2) Polymerization reaction: the mixture formed in the step (1) is polymerized under the catalysis of a catalyst to generate a trioxymethylene aqueous solution, and after the polymerization, the product is the trioxymethylene aqueous solution and a small amount of unvaporized dehydrating agent; the catalyst is a strong acid resin catalyst;
(3) And (3) product fractionation: fractionating the product formed in step (2) under heating to obtain a gas phase and a liquid phase; the gas phase is the dehydrating agent and a small amount of water existing in the product, a part of the dehydrating agent and a part of the water are returned to the step (1) for recycling after condensation, and the liquid phase is the finished product of trioxymethylene and is recovered.
2. Method according to claim 1, characterized in that the method comprises in particular the following steps:
(1) Azeotropic dehydration: the formaldehyde aqueous solution and the dehydrating agent are led into a tube side of a heater (6) by a feed pump (7) for heating, and heated to 50-100 ℃ under normal pressure or micro-positive pressure, then reach azeotropic temperature, and led into an azeotropic dehydration section of an azeotropic catalytic reaction tower (1) by a feed port 1C for azeotropic dehydration, thereby achieving the purpose of concentrating formaldehyde, and forming two phases in the tower under the action of an azeotropic principle: the gas phase is water and partial dehydrating agent, and the liquid phase is dehydrated and concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent; wherein: the gas phase rises to the top of the tower and is discharged from a gas phase outlet 1A, and condensed by a condenser I (2) to form liquid phase water and a dehydrating agent, the liquid phase water and the dehydrating agent discharge the dehydrated water through a water outlet under the double functions of a coalescer (4) and static layering in a reflux tank I, and the liquid phase dehydrating agent is pumped to a first reflux port 1B by a reflux pump I so as to be totally refluxed to an azeotropic catalytic reaction tower for recycling; the dehydrated and concentrated formaldehyde aqueous solution and a small amount of unvaporized dehydrating agent can downwards flow into the catalytic section of the azeotropic catalytic reaction tower (1) under the action of gravity;
(2) Polymerization reaction: the dehydrated and concentrated formaldehyde aqueous solution descends to a tubular bed of a catalytic section, and is polymerized under the catalysis of a catalyst in the tubular to generate trioxymethylene aqueous solution, and after the polymerization, the product is the trioxymethylene aqueous solution and a small amount of unvaporized dehydrating agent; the product continuously descends to the bottom of the tower under the action of gravity, is discharged from a discharge port 1E and is guided into a finished product rectifying tower (8) from a feed port 8A; the heating liquid inlet 1D of the catalytic section is connected with a hot water pump, hot water provided by the hot water pump enters the shell side of the catalytic section to provide temperature for polymerization reaction in the tube array, and the heating liquid outlet 1F is connected with a hot water collecting system;
(3) And (3) product fractionation: after the product formed in the step (2) is introduced into a finished rectifying tower (8), fractionation is carried out in a heating state of a reboiler (9) to obtain a gas phase and a liquid phase; the gas phase is a dehydrating agent and a small amount of water existing in the product, the dehydrating agent and the small amount of water are discharged from a gas phase outlet 8C and enter a condenser II (10) for condensation, the dehydrating agent and the small amount of water obtained by condensation sequentially flow through a reflux tank II (11) and a reflux pump II (12) and are divided into three paths, one path is connected with a reflux port 8B, the other path is connected with a first reflux liquid inlet 1B of an azeotropic catalytic tower, and the third path is connected with a second reflux liquid inlet 1G communicated with the lowest part distributor of a tubular bed and continuously enters the tubular bed for continuous dehydration and recycling; the liquid phase obtained at the bottom of the tower is the pure trioxymethylene product, which is discharged and collected by a discharge hole 8D.
3. The method according to claim 2, wherein in the step (1), the mass ratio of the dehydrating agent to formaldehyde in the aqueous formaldehyde solution is 1 to 10:1, a step of; the mass fraction of formaldehyde in the formaldehyde aqueous solution is 30-55%.
4. The method according to claim 2, wherein in the step (2), the hot water is supplied by the hot water pump at a temperature of 80 to 120 ℃ to ensure a polymerization reaction temperature of 70 to 110 ℃ in the column bed.
5. The method according to claim 2, wherein in step (3), the finishing rectification column (8) is operated under the following conditions: overhead temperature: 30-110 ℃; bottom temperature: 80-180 ℃; operating pressure: 0.01-1.5Mpa; the dehydrating agent obtained by condensation and a small amount of water are refluxed into the finished product rectifying tower from a reflux port 8B, and the reflux ratio is 0.1-2.0.
6. The utility model provides a device of azeotropic catalytic reaction synthesis trioxymethylene, includes feed pump (7), heater (6), azeotropic catalytic reaction tower (1), finished product rectifying column (8) that link to each other in proper order, and raw materials formaldehyde aqueous solution and dehydrating agent enter into the tube side internal heating of heater (6) at first, then enter into the azeotropic catalytic reaction tower and carry out the dehydration, and the result of dehydration divide into two phases: the gas phase rises to enter the azeotropic dehydration section and flows out of the tower, and the liquid phase falls into the catalytic section under the action of gravity to carry out polymerization reaction; introducing the polymerization product into a rectifying tower (8), and fractionating to obtain a product trioxymethylene finished product; the method is characterized in that:
the feed pump (7) is provided with an inlet 7A and an outlet 7B, wherein: the inlet 7A is connected with a device capable of providing raw formaldehyde aqueous solution and a dehydrating agent;
the heater (6) is provided with an inlet 6A and an outlet 6B, wherein: the inlet 6A is connected with the outlet 7B of the feed pump; the azeotropic catalytic reaction tower (1) is characterized in that a gas phase outlet 1A (101) is formed in the top of the azeotropic catalytic reaction tower, a discharge hole 1E (105) is formed in the bottom of the azeotropic catalytic reaction tower, a first reflux inlet 1B (102) is formed in the upper part of the side wall, a feed inlet 1C (103) is formed in the middle of the azeotropic catalytic reaction tower, a heating liquid outlet 1F (106) and a heating liquid inlet 1D (104) are formed in the middle of the azeotropic catalytic reaction tower, a second reflux inlet 1G (107) is formed in the lower part of the azeotropic catalytic reaction tower, and the position of the heating liquid inlet 1D is lower than that of the heating liquid outlet 1F; wherein: the feed inlet 1C is connected with an outlet 6B of the heater (6); the gas phase outlet 1A is sequentially connected with a condenser I (2), a reflux tank I (3) and a reflux pump I (5), and the pump outlet of the reflux pump I is connected with a first reflux liquid inlet 1B; the heating liquid inlet 1D is connected with a hot water pump, and the heating liquid outlet 1F is connected with a hot water collecting system;
the reflux tank I (3) is provided with a liquid inlet, a liquid outlet and a water outlet, and a coalescer (4) is arranged in the reflux tank I; wherein, the liquid inlet is connected with the outlet of the condenser I (2), the liquid outlet is connected with the pump inlet of the reflux pump I (5), the water outlet is connected with the wastewater treatment system, the gas phase is condensed by the condenser I to form a liquid phase, and the liquid phase enters the reflux tank I and the dehydrated water is discharged from the water outlet under the double functions of the coalescer and the static layering;
finished product rectifying column (8), the top be equipped with gaseous phase export 8C, the bottom is equipped with finished product discharge gate 8D, the lateral wall top is equipped with the return port 8B, the middle part is equipped with feed inlet 8A, wherein: the feed inlet 8A is connected with the discharge outlet 1E of the azeotropic catalytic reaction tower; the gas phase outlet 8C is sequentially connected with a condenser II (10), a reflux tank II (11) and a reflux pump II (12); the pump outlet of the reflux pump II (12) is divided into three paths, one path is connected with the reflux port 8B, the other path is connected with the first reflux inlet 1B of the azeotropic catalytic tower, and the third path is connected with the second reflux inlet 1G of the azeotropic catalytic tower, and continuously enters the azeotropic catalytic tower for continuous dehydration and recycling; the discharge hole 8D is connected with a device for collecting or receiving finished trioxymethylene;
and a reboiler (9) is arranged below the side wall of the finished product rectifying tower (8).
7. The device according to claim 6, wherein the azeotropic catalytic reaction tower (1) is provided with a demister (13) at the inner top end, the lower part of the demister (13) comprises an azeotropic dehydration section positioned at the upper part and a catalytic section positioned at the lower part, and the top of the azeotropic dehydration section is provided with a distributor (14) and a grating plate (19) from top to bottom in sequence; the top of the catalytic section is sequentially provided with a distributor (14) and a grating plate (19) from top to bottom, and the bottom of the catalytic section is sequentially provided with the distributor (14), a cushion layer (18) and the grating plate (19) from top to bottom; the azeotropic dehydration section is provided with a tower internal part (15), and the tower internal part (15) comprises any one of structured packing or tower plates; the tower internal part (15) is selected from a structured packing, the number of the structured packing filling sections is N, the number of the structured packing filling sections is less than or equal to 1 and less than or equal to 100, the height of each section is 1-3 meters, a distributor (14) and a grating plate (19) are arranged between each section, and the distributor (14) is arranged on the grating plate (19); or the tower internal part (15) is selected from a tower plate, wherein the number of the tower plates is M, and M is more than or equal to 1 and less than or equal to 100; the catalytic section comprises a tubular bed (16), the number of the catalytic section is N, N is more than or equal to 1 and less than or equal to 10, and a distributor (14), a cushion layer (18) and a grating plate (19) are sequentially arranged between the sections from top to bottom;
the tube array bed (16) comprises a plurality of vertically arranged tube arrays (17), a module catalyst (40) is filled in the tube arrays (17), a heating liquid flow channel is arranged between the outer wall of the tube arrays (17) and the inner wall of the reaction tower (1), the top and the bottom of the tube array bed (16) are respectively provided with a closed baffle plate for closing the upper end and the lower end of the heating liquid channel, and a plurality of openings are arranged on the baffle plates and are communicated with two openings of the corresponding tube arrays (17); the reaction raw materials flowing down from the azeotropic dehydration section sequentially pass through each distributor (14), a cushion layer (18), a grating plate (19) and a tube array (17) in the multi-section catalytic section to be discharged;
the top of the azeotropic catalytic reaction tower (1) is provided with a gas phase outlet 1A (101) and a discharge hole 1E (105) at the bottom, a heating liquid inlet 1D (104) is arranged at the bottom of a column bed (16) on the side wall of the reaction tower (1), a heating liquid outlet 1F (106) is arranged at the top of the column bed (16) on the side wall of the azeotropic catalytic reaction tower (1) opposite side, a distributor (14) at the uppermost part of the azeotropic catalytic reaction tower (1) is communicated with a first backflow liquid inlet 1B (102) arranged on the side wall of the azeotropic catalytic reaction tower, a distributor (14) at the lowermost part of the azeotropic catalytic reaction tower is communicated with a second backflow liquid inlet 1G (107) arranged on the side wall of the azeotropic catalytic reaction tower, and a distributor (14) above a tower internal part (15) in the middle is communicated with a feed inlet 1C (103) arranged on the side wall of the azeotropic catalytic reaction tower (1).
8. The device according to claim 7, wherein the cushion layer (18) is a five-layer layered structure formed by combining quartz sand or porcelain balls with different particle sizes, and the five-layer layered structure is five-level grading: the granularity of the uppermost layer is close to or slightly larger than that of the catalyst, the granularity of the lowermost layer is slightly larger than the gap dimension of the grating plate (19), three layers are arranged in a mode of gradually increasing from top to bottom and the upper and lower granularity are connected, and the thickness of each layer is 5-15 cm; the foam remover (13), the distributor (14) and the grating plate (19) are made of stainless steel.
9. The device according to claim 7, wherein each catalytic section is provided with a heating liquid inlet 1D (104) and a heating liquid outlet 1F (106); the module catalyst (40) comprises a catalyst, a wire mesh (402) and a wire mesh corrugated plate (403), wherein the module catalyst (40) is formed by arranging the wire mesh (402) and the wire mesh corrugated plate (403) in parallel at intervals, a catalyst layer (401) is formed by bearing the catalyst particles between the two wire mesh (402), and the catalyst particles in the catalyst layer (401) are separated by the wire mesh corrugated plate (403); the catalyst layers (401) in the module catalyst (40) are arranged at intervals.
10. The apparatus according to claim 7, wherein the catalyst in the module catalyst (40) is a strongly acidic resin catalyst; the dehydrating agent added into the azeotropic catalytic reaction tower from the feed pump is any one of dichloroethane, benzene and cyclohexane or a mixture of two or more of them in any proportion.
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| CN106831380A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院成都有机化学有限公司 | The method of formalin dehydration concentration |
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| US4962235A (en) * | 1988-04-07 | 1990-10-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing high purity formaldehyde |
| CN106831380A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院成都有机化学有限公司 | The method of formalin dehydration concentration |
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