CN116651323A

CN116651323A - Plug flow type reaction device for high-pressure reaction process and construction method thereof

Info

Publication number: CN116651323A
Application number: CN202310549717.0A
Authority: CN
Inventors: 梁经永; 陈道伟; 胡家啟; 黄亮兵; 周伟; 张官芳
Original assignee: ZHEJIANG KAIHUA SYNTHETIC MATERIAL CO Ltd
Current assignee: ZHEJIANG KAIHUA SYNTHETIC MATERIAL CO Ltd
Priority date: 2023-05-16
Filing date: 2023-05-16
Publication date: 2023-08-29

Abstract

The application belongs to the technical field of chemical reaction equipment, and in particular relates to a plug flow type reaction device for a high-pressure reaction process and a construction method thereof, wherein the plug flow type reaction device comprises: at least one reaction unit having a reaction unit inlet and a reaction unit outlet; the reaction unit is provided with a spiral channel which is spiral in the horizontal direction, the reaction material enters the spiral channel through the inlet of the reaction unit, and after the plug flow reaction is carried out in the spiral channel, the reaction material is discharged through the outlet of the reaction unit.

Description

Plug flow type reaction device for high-pressure reaction process and construction method thereof

Technical Field

The application belongs to the technical field of chemical reaction equipment, and particularly relates to a plug flow type reaction device, in particular to a plug flow type reaction device for a high-pressure reaction process and a construction method thereof.

Background

At present, high-temperature gas-phase condensation reaction and direct-method fluidized bed processes are mainly adopted for large-scale production of aryl or phenyl chlorosilane at home, the reaction temperature of the two processes is up to more than 500 ℃, expensive high-nickel chromium alloy manufacturing reaction equipment is needed, the generation of polychlorinated biphenyl cannot be avoided, various reaction byproducts are caused, the product purification difficulty is high, and meanwhile, the problems of frequent pipeline coking and blocking faults, serious high-temperature chlorine corrosion and high overhaul and maintenance costs of the reaction equipment exist. Among them, the direct fluidized bed process for producing aryl or phenylchlorosilane requires the use of a metal catalyst, which is more likely to produce polychlorinated biphenyl and has serious environmental pollution. Therefore, when the chlorosilane product obtained by the two processes is used for producing downstream end products, the chlorosilane product must be treated by long-time treatment of metallic sodium or other high-difficulty high-cost high-risk processes, so that the content of dangerous poison polychlorinated biphenyl contained in the chlorosilane product can be reduced to below 0.5ppm to meet international standards, otherwise, the market is strictly limited. In addition, the Grignard method and the sodium condensation method are adopted to produce aryl or phenyl chlorosilane and downstream products thereof, but the processes have the defects of high risk, high cost, difficult production capacity amplification and the like.

The research finds that: the high-pressure liquid-phase non-catalytic condensation reaction is utilized to produce aryl or phenyl chlorosilane, although the high-pressure condition of 15-20 MPa is needed, the reaction temperature is lower, the temperature can be lower than 350 ℃, the types of byproducts in the reaction process are few, the product is easy to purify, meanwhile, the generation of high-toxicity polychlorinated biphenyl can be avoided, the byproducts of high-boiling matters are easy to treat and utilize, the dangerously wasted high-boiling slag slurry is little, and a large amount of aryl hydrogen-containing dichlorosilane can be produced by the process and used for producing special organosilicon monomers; particularly, when the reaction temperature is controlled below 330 ℃, the byproduct aryl hydrogen-containing dichlorosilane can be better, but the reaction speed becomes very slow, if the mass production is realized, a long thick-wall pipeline reactor is required to realize the plug flow reaction to obtain the necessary reaction conversion rate, but because the reaction pipeline is required to resist hydrogen embrittlement and high-temperature chlorine corrosion, the manufacturing cost of the plug flow high-pressure reactor is very high, so that the mass production of aryl or phenyl chlorosilane by using the high-pressure liquid-phase non-catalytic condensation reaction of chlorinated aromatic hydrocarbon and hydrogen-containing chlorosilane is not realized at home. Similarly, the method for synthesizing aryl or phenyl chlorosilane by catalyzing benzene and hydrogen-containing chlorosilane under high pressure of 10MPa by adopting boron trifluoride or boron trichloride with low boiling point has the advantages of low reaction process temperature, higher yield, capability of avoiding generating polychlorinated biphenyl and easy purification of products, but also has the defect of low reaction speed, and when a tubular reactor is adopted, auger screws, namely screw conveyors, are also required to be arranged in a reaction tube, so that the contact mass transfer effect of a gas catalyst and reaction liquid is maintained, a large amount of stainless steel is consumed, and the difficulty and the cost for constructing the production device are high. In summary, the high-pressure risk exists in the reaction process, so that the construction cost of the reaction device is high, the difficulty is high, and the high-pressure liquid phase non-catalytic condensation method, the catalytic dehydrogenation method and other high-pressure processes for preparing the chlorosilane are difficult to be adopted in industry all the time.

In the existing reaction device, the plug flow reactor is adopted to be beneficial to improving the selectivity and the conversion rate of synthesizing the aryl chlorosilane by high-pressure liquid phase reaction, and the operation process is stable and continuous, the operation is simple, and the safety of the high-pressure process is easy to be ensured. In general, the plug flow reactor of the existing high-pressure reaction process is implemented by adopting a tubular reactor, which is beneficial to improving the heat exchange efficiency, and is beneficial to reducing the construction cost for the rapid reaction process, but when the tubular reactor is used for the slow high-pressure reaction process, the tubular reactor has high requirements on the materials and welding of equipment, has multiple consumables, is difficult to compactly arrange, has high construction cost and high safety risk, and is not suitable for the high-pressure reaction process and the catalytic dehydrogenation method for producing aryl or phenyl chlorosilane.

In view of the above, it is an urgent technical problem to be solved by those skilled in the art to provide a safe, efficient and low-construction-cost plug flow reaction device and construction method thereof, which can be applied to the high-pressure reaction process for producing aryl or phenyl chlorosilane, and to promote the development of the high-pressure reaction process for producing aryl or phenyl chlorosilane. ,

disclosure of Invention

The invention aims at solving the technical problems and provides a safe, efficient and low-construction-cost plug flow type reaction device for producing chlorosilane by a high-pressure reaction process and a construction method thereof.

In view of this, the present invention provides a method of constructing a plug flow reaction apparatus for a high pressure reaction process, the plug flow reaction apparatus comprising:

at least one reaction unit having a reaction unit inlet and a reaction unit outlet;

the reaction unit is provided with a spiral channel which is spiral in the horizontal direction, the reaction material enters the spiral channel through the inlet of the reaction unit, and after the plug flow reaction is carried out in the spiral channel, the reaction material is discharged through the outlet of the reaction unit.

Further, the spiral channel is a spiral reaction channel extending along an archimedes spiral or equidistant spiral.

Further, the spiral channel includes:

the concentric ring channels are arranged at equal intervals, blind plates are arranged on the vertical surfaces of the concentric ring channels in the concentric ring channels, the same concentric ring channel is divided into non-communicated circular ring channels through the blind plates, and one side of each blind plate is provided with a communication port which is communicated with the adjacent inner ring channel and outer ring channel;

the reaction fluid sequentially flows through all layers of concentric circular loops through the communication ports, and flows to the inner layers of the concentric circular multi-layer loops or flows to the outer layers;

Reactant fluid in adjacent inner and outer annular circuits can flow in the same or opposite directions.

Further, the spiral channel is manufactured by adopting a straight pipe with a round or square cross section to carry out pipe bending processing.

Further, the reaction unit includes:

the device comprises two spiral channels which are arranged side by side, wherein one of the spiral channels is marked as a positive spiral channel, the other one of the spiral channels is marked as a negative spiral channel, the positive spiral channel and the negative spiral channel are mutually communicated, and the flowing directions of reaction materials in the positive spiral channel and the negative spiral channel are opposite;

the reaction materials enter the reaction unit through the inlet of the reaction unit, flow through the positive spiral channel and the reverse spiral channel in sequence for reaction, and are discharged through the outlet of the reaction unit.

Further, the cross sections of the positive spiral channel and the negative spiral channel are rectangular cross sections with the width dimension being larger than the height dimension.

Further, the plug flow reaction device further comprises:

an inner cylinder disposed in a vertical direction;

an outer cylinder circumferentially disposed around the outer periphery of the inner cylinder;

an annular gap between the inner cylinder body and the outer cylinder body forms an annular gap channel, and a temperature control medium flows in the annular gap channel to regulate and control the temperature of the reaction unit;

The reaction materials and the temperature control medium enter from the lower end of the plug flow type reaction device, then gradually upwards and are discharged from the upper end of the plug flow type reaction device.

Further, the plug flow reaction device further comprises:

the upper end socket and the lower end socket are oppositely arranged at two ends of the inner cylinder body;

the upper end enclosure and the lower end enclosure are flat end enclosures or dish-shaped end enclosures.

Further, the inner cylinder body is prepared from 316L or 304L stainless steel;

the outer cylinder body is prepared from hydrogen embrittlement resistant carbon steel containing chromium and molybdenum elements, and stainless steel 321 or 309 is deposited on the inner wall of the outer cylinder body; or the outer cylinder is a stainless steel/carbon steel composite cylinder prepared by an explosion composite method.

Further, the reaction unit includes:

a spiral separator spirally provided in the reaction unit, the spiral channel being formed by curling of the spiral separator, the spiral separator located outside the reaction unit being referred to as an outer separator, which constitutes an outer wall of the reaction unit;

wherein, the spiral baffle plate positioned in the reaction unit is made of a thin-wall stainless steel plate with the thickness of 1.5-3 mm;

the outer partition plate is made of plates with the thickness of more than 15mm, and the outer partition plate is made of a thick carbon steel plate of double-sided composite stainless steel.

Further, the plug flow reaction device includes:

the reaction zone main body of the plug flow type reaction device is formed by sequentially connecting the reaction unit inlet and the reaction unit outlet in series.

A plug flow type reaction device for a high-pressure reaction process is prepared according to the construction method.

The plug flow type reaction device and the construction method thereof have the advantages of safety, high efficiency and low construction cost.

Drawings

FIG. 1 is a schematic top view of a reaction unit according to the present invention;

FIG. 2 is a schematic structural view of a plug flow reaction device according to the present invention;

FIG. 3 is a flow chart of a process for producing chlorosilanes in series using a plurality of plug flow reaction apparatus of the present invention;

FIG. 4 is a flow chart of a process for producing chlorosilane by catalytic dehydrogenation using a plurality of plug flow reaction devices of the present invention in series;

FIG. 5 is another schematic top view of the reaction unit of the present invention.

The label in the figure is:

1. a reaction unit; 101. a positive helical channel; 102. a reverse helical channel; 103. an inlet of the reaction unit; 104. an outlet of the reaction unit; 105. a junction region; 106. a spiral separator; 107. an outer partition; 2. an inner cylinder; 3. an outer cylinder; 4. a reaction material inlet; 5. a reaction material outlet; 6. an annular gap passage; 7. a temperature control medium inlet; 8. a temperature control medium outlet; 9. a bellows expansion joint; 10. concentric multi-layer loops; 11. a blind plate; 12. and a communication port.

Detailed Description

The technical solutions of the embodiments of the present application will be clearly described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which are obtained by a person skilled in the art based on the embodiments of the present application, fall within the scope of protection of the present application.

In the description of the present application, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments in accordance with the present application. For ease of description, the dimensions of the various features shown in the drawings are not drawn to actual scale. Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.

It should be noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged, as appropriate, such that embodiments of the present application may be implemented in sequences other than those illustrated or described herein, and that the objects identified by "first," "second," etc. are generally of a type, and are not limited to the number of objects, such as the first object may be one or more. Furthermore, in the description and claims, "and/or" means at least one of the connected objects, and the character "/", generally means that the associated object is an "or" relationship.

It should be noted that, in the description of the present application, the terms like "front, rear, upper, lower, left, right", "horizontal, vertical, horizontal", and "top, bottom", etc. generally refer to the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are merely for convenience of describing the present application and simplifying the description, and these orientation terms do not indicate and imply that the apparatus or elements referred to must have a specific orientation or be constructed and operated in a specific orientation, and thus should not be construed as limiting the scope of the present application; the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.

It should be noted that, in the present application, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Furthermore, it should be noted that the scope of the methods and apparatus in the embodiments of the present application is not limited to performing the functions in the order shown or discussed, but may also include performing the functions in a substantially simultaneous manner or in an opposite order depending on the functions involved, e.g., the described methods may be performed in an order different from that described, and various steps may be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.

A method of constructing a plug flow reaction apparatus for producing chlorosilanes in a high pressure reaction process, the plug flow reaction apparatus comprising:

At least one reaction unit 1, said reaction unit 1 having a reaction unit inlet 103 and a reaction unit outlet 104;

the reaction unit 1 is provided with a spiral channel, namely a reaction pipeline of the plug flow type reaction device, reaction materials enter the spiral channel through the inlet 103 of the reaction unit, and are discharged through the outlet 104 of the reaction unit after plug flow reaction is carried out in the spiral channel.

Preferably, the spiral channel is a reaction channel extending in a vertical direction and spirally formed in a horizontal direction.

As some embodiments of the present application, the reaction unit 1 includes two spiral channels arranged in parallel side by side, one of which is denoted as a positive spiral channel 101, and the other as a negative spiral channel 102, and the positive spiral channel 101 and the negative spiral channel 102 are in communication with each other; the reaction materials enter the reaction unit 1 through the inlet 103 of the reaction unit, flow through the positive spiral channel 101 and the reverse spiral channel 102 in sequence for reaction, and are discharged through the outlet 104 of the reaction unit.

At this time, the structure of the forward spiral path 101 and the reverse spiral path 102 is similar to two spiral paths formed by two parallel rolls of sheet material.

In the present application, the form and spiral direction of the forward spiral channel 101 and the reverse spiral channel 102 are substantially identical, and the difference is mainly that the flow direction of the reaction materials in the forward spiral channel 101 and the reverse spiral channel 102 is different, which are referred to as the forward spiral channel 101 and the reverse spiral channel 102, respectively, for the sake of clarity of description of the present application, and when the reaction materials are advanced in the forward spiral channel 101 in a clockwise or counterclockwise direction, they are advanced in the reverse spiral channel 102 in the opposite direction.

Further, the plug flow reaction device includes:

the reaction units 1 are sequentially connected in series through the reaction unit inlet 103 and the reaction unit outlet 104 to form a reaction zone main body of the plug flow type reaction device.

As some embodiments of the present application, the reaction unit 1 is rolled into two spiral channels by two parallel plates arranged in the vertical direction, and the obtained positive spiral channel 101 and the negative spiral channel 102 extend in the vertical direction and are spiral in the horizontal direction.

Preferably, the reaction unit 1 is rolled into two spiral channels along archimedes 'spiral or equidistant spiral by two parallel sheets, so that the resulting forward and reverse spiral channels 101 and 102 will also extend along archimedes' spiral or equidistant spiral.

Wherein the forward spiral channel 101 and the reverse spiral channel 102 have a center end close to the center area of the reaction unit 1 and an edge end close to the edge of the reaction unit 1, the reaction unit inlet 103 is disposed at the center end of the forward spiral channel 101, the reaction unit outlet 104 is disposed at the center end of the reverse spiral channel 102, the edge ends of the forward spiral channel 101 and the reverse spiral channel 102 are communicated, and an intersection area 105 is formed at the communication position of the forward spiral channel 101 and the reverse spiral channel 102, so that the movement track of the reaction material in the reaction unit 1 is as follows: first entering the center end of the positive spiral channel 101 through the reaction unit inlet 103, and then proceeding spirally along the extending path of the positive spiral channel 101 until reaching the edge end of the positive spiral channel 101; with the change of the channel direction, turbulence is generated at the junction 105 of the edge end of the forward spiral channel 101 and the edge end of the reverse spiral channel 102, and then the mixture advances along the extending path of the reverse spiral channel 102 in the reverse direction until reaching the center end of the reverse spiral channel 102, and then is discharged through the reaction unit outlet 104, thereby completing the movement in the reaction unit 1 and entering the next reaction unit 1.

Preferably, the plug flow type reaction device comprises a plurality of reaction units 1, and the plurality of reaction units 1 are stacked in the vertical direction and connected in series.

Still further, the reaction unit 1 includes:

a spiral separator 106 spirally provided in the reaction unit 1, the spiral passages such as the forward spiral passage 101 and the reverse spiral passage 102 being formed by crimping of the spiral separator 106.

Each reaction cell 1 will then comprise two spiral baffles 106 arranged substantially parallel except for the central and edge regions.

For the sake of clarity of the description of the present application, the spiral partition 106 located outside the reaction unit 1 is referred to as an outer partition 107, which constitutes the outer wall of the reaction unit 1.

Preferably, a plurality of reaction units 1 are stacked in the vertical direction in the plug flow type reaction device, and the reaction unit outlet 104 of the lower reaction unit 1 is connected with the reaction unit inlet 103 of the upper reaction unit 1 to form a cylindrical reaction zone main body.

Further, the plug flow reaction device further comprises:

an inner cylinder 2 disposed in a vertical direction;

an outer cylinder 3 disposed around the outer periphery of the inner cylinder 2;

An annular gap between the inner cylinder body 2 and the outer cylinder body 3 forms an annular gap channel 6, and a temperature control medium flows in the annular gap channel 6 to regulate and control the temperature of the reaction unit 1.

As some embodiments of the present application, the inner cylinder 2 is a rearranged inner cylinder wall different from the outer partition 107, and may also be directly integrally formed by the outer partition 107 stacked together.

Further, the reaction materials and the temperature control medium enter from the lower end of the plug flow type reaction device, gradually upwards and then are discharged from the upper end of the plug flow type reaction device.

Further, a reaction material inlet 4 and a reaction material outlet 5 are respectively arranged at the lower end and the upper end of the plug flow type reaction device, and the reaction material enters the reaction unit 1 at the lowest layer from the lower end of the plug flow type reaction device through the reaction material inlet 4 and then is gradually upwards discharged from the reaction material outlet 5 at the upper end of the plug flow type reaction device.

Correspondingly, a temperature control medium inlet 7 and a temperature control medium outlet 8 are respectively arranged at the lower end and the upper end of the plug flow type reaction device, and the temperature control medium enters the annular gap channel 6 from the lower end of the plug flow type reaction device and then gradually upwards is discharged from the temperature control medium outlet 8 at the upper end of the plug flow type reaction device.

Preferably, the temperature control medium is a chlorinated aromatic hydrocarbon.

Still further, the plug flow reaction device further includes:

the upper seal head and the lower seal head are oppositely arranged at two ends of the inner cylinder body 2.

It should be noted that, the upper end enclosure and the lower end enclosure may be flat end enclosures, but because the pressure of the main body of the reaction zone is larger, the flat end enclosures need to be thick to withstand voltage, which affects economy, so the upper end enclosure and the lower end enclosure may also be dish-shaped end enclosures, and the dish-shaped end enclosures may be subjected to a large pressure difference to reduce the thickness of the upper end enclosure and the lower end enclosure.

When in use, the reaction materials can firstly enter the lower sealing head, then enter the reaction unit 1 at the lowest layer through the reaction unit inlet 103, gradually upwards, finally enter the upper sealing head through the reaction unit outlet 104 of the reaction unit 1 at the highest layer, and finally be discharged out of the plug flow type reaction device.

As some embodiments of the present application, when the upper and lower seal heads are provided, the reaction unit inlet 103 and the reaction unit outlet 104 may be provided in the central region of the reaction unit 1 in the aforementioned manner, or may be provided instead at the edge ends of the forward spiral channel 101 and the reverse spiral channel 102, and at this time, the edge ends of the forward spiral channel 101 and the reverse spiral channel 102 are not communicated, the central ends are communicated, and the reaction material first enters the reaction unit 1 through the reaction unit inlet 103 located at the edge end of the forward spiral channel 101, then flows from the outside to the center of the reaction unit 1 along the forward spiral channel 101, then flows from the center to the outside through the reverse spiral channel 102, and finally is discharged through the reaction unit outlet 104 provided at the edge end of the reverse spiral channel 102.

The application adopts the novel plug flow type reaction device to reduce the construction cost of the reaction device with high pressure, low speed and low heat effect, and when the device is used for producing chlorosilane, such as aryl chlorosilane or phenyl chlorosilane, especially for high pressure technology, such as high pressure liquid phase non-catalytic condensation method and catalytic dehydrogenation method for producing chlorosilane, cheap stainless steel material can be selected to replace expensive material, the total consumption of stainless steel is greatly reduced, and meanwhile, the welding requirement of high standard is also greatly reduced.

Of course, besides being used for producing chlorosilane, the plug flow reaction device of the application can also be used for producing other chemical products.

Compared with the existing reactor system for producing phenyl chlorosilane by a low-pressure high-temperature gas phase condensation method, the plug flow reaction device provided by the application has the advantages that: the construction cost is close, but the running and maintenance cost of the plug flow reaction device can be lower, and the large-scale production can be easily realized by combining the design of the process flow on the basis of improving the reactor structure.

When the flat plug flow type reaction device is used, the flat plug flow type reaction device can be quickly applied to the production process of carrying out high-pressure liquid phase condensation reaction on chlorinated aromatic hydrocarbon and hydrogen-containing chlorosilane to produce aryl chlorosilane on a large scale, and the heat release in the chemical reaction process is less, the reaction speed is low, the reaction heat is easy to remove, and when the flat plug flow type reaction device shown in the figures 1-2 is used for carrying out the reaction, a plurality of reaction units in the flat plug flow type reaction device can be connected in series from bottom to top to obtain an ultra-long flow channel so as to meet the residence time required by the slow reaction, thereby avoiding the difficult problem that the compact arrangement is difficult to realize by adopting an ultra-long tubular reactor.

The realization of the horizontal spiral channel is the same as the principle of the spiral plate heat exchanger, and the channel sections of the positive spiral channel 101 and the reverse spiral channel 102 can adopt square shapes to save materials and reduce flow resistance.

Preferably, the positive spiral channel 101 and the negative spiral channel 102 have rectangular cross sections with a width dimension in the horizontal direction larger than a height dimension in the vertical direction, which is more advantageous for optimizing mass transfer.

In addition, the mass transfer efficiency of the reaction fluid can be enhanced by installing a shaftless auger ribbon in the spiral channel of the large-capacity plug flow reaction device, and the auger ribbon can be not installed in the spiral flow channel of the small-capacity plug flow reaction device.

As some embodiments of the present application, the outer partition 107 is cylindrical, and is made of a plate with a thickness of more than 15mm, so that the outer partition can withstand a larger pressure difference, and has higher safety; meanwhile, the outer partition 107 may be made of a thick carbon steel plate with double-sided composite stainless steel to reduce the cost, while the spiral partition 106 inside the reaction unit 1 needs to bear small pressure difference, and may be made of a thin stainless steel plate with 1.5-3 mm.

As some embodiments of the present application, only the two reaction units 1 at the very top and the very bottom, respectively, must withstand a high pressure difference, and thus, it is necessary to manufacture them using thick plates, and the pressure difference that the remaining reaction units 1 withstand is relatively small, and the thickness thereof can be suitably reduced.

As some embodiments of the present application, for a small capacity plug flow reaction apparatus, one of the simpler and more efficient methods of making the forward spiral channel 101 and the reverse spiral channel 102 is: the main bodies of the middle areas of the precisely formed positive spiral channel 101 and the precisely formed negative spiral channel 102 are respectively obtained by a numerical control roll bending forming machine directly adopting a standard stainless steel square straight pipe with the thickness of 3mm, and the spiral channel at the central part is required to be assembled and welded with the main body roll-bent by the straight square pipe after being assembled and welded by adopting a steel plate forming part due to overlarge torsion degree, so that the spiral channel forming part is obtained. The precise equidistant spiral forming process can be realized by referring to a variable-curvature numerical control roll bending machine of Guangzhou high-spectrum mechanical science and technology limited company. And then arranging the two obtained spiral channel forming pieces on the upper and lower adjacent unit layers, carrying out cross stacking, and carrying out seal welding and fixing on gaps at the stacking position, so that the number of the spiral channels with closed periphery is multiplied, and carrying out welding and sealing processing on the spiral channel forming pieces through local structures, such as butt joint seal welding with an outer partition plate 107, structure seal welding of a junction area 105 and structure seal welding of a reaction unit inlet 103 and a reaction unit outlet 104 at the center, wherein the outer partition plate 107 can be realized through an integral pressure-resistant cylinder specially processed by sections, a large number of high-requirement large-thickness welding seams required by step-by-step butt welding are avoided, the requirement on the welding strength of step-by-step butt joint seal welding with the spiral channel forming pieces is low, and the rapid construction can be realized through laser welding. The spiral channels obtained by the layer-by-layer processing method have the advantage that adjacent channels are only separated by metal wall surfaces with smaller thickness, so that heat can be easily transferred outwards or inwards. Thus, the wall surfaces of all the spiral channels are in honeycomb-shaped crossed interconnection and form an integrated reaction zone main body assembly with the outer partition plate 107, so that the structure is stable and the rigidity is good, and serious vibration damage caused by gas-liquid mixed flow can be prevented.

As some embodiments of the application, the annular gap width of the annular gap channel 6 is 10-20 mm, and the high-pressure liquid chlorinated aromatic hydrocarbon flows to take away the reaction heat emitted by the wall surface of the inner cylinder 2.

In addition, the reaction temperature is below 350 ℃, so that the components in the inner cylinder body 2 can be made of low-cost stainless steel, such as 316L material, to bear long-term chlorine corrosion and hydrogen embrittlement damage. The outer cylinder 3 needs to bear the high temperature and high pressure in the reaction device, and the design can refer to hydrogenation reactors in petrochemical industry and coal chemical industry for material selection, for example, the main body of the outer cylinder 3 uses hydrogen embrittlement resistant carbon steel containing chromium and molybdenum elements, and stainless steel 321 or 309 is deposited on the inner wall of the outer cylinder to meet the long-term hydrogen embrittlement resistance and chlorine corrosion resistance requirements.

Therefore, the application can reduce the construction cost of the reaction device with high pressure, low speed and low heat effect by adopting the novel plug flow reactor, and when the reactor is used for producing aryl chlorosilane or phenyl chlorosilane, cheap stainless steel materials such as 304, 316 stainless steel and the like can be selected to replace expensive materials such as high nickel-chromium alloy and the like used by the prior reactor, and the consumption of the stainless steel is greatly reduced, thereby reducing the overall cost of the plug flow reaction device; meanwhile, the plug flow type reaction device can greatly reduce the high-standard welding requirement, and has the construction cost close to that of a reactor system for producing phenylchlorosilane by a low-pressure high-temperature gas phase condensation method, but the plug flow type reaction device has lower operation and maintenance cost, and is easy to realize a large-scale production device by the design and cooperation of the reactor structure optimization and the process flow.

As some embodiments of the application, the corrugated expansion joint 9 is arranged in the plug flow type reaction device to compensate the influence caused by the asynchronous thermal expansion of the inner cylinder and the outer cylinder, so as to ensure the connection safety of the reactant outlet pipes.

Further, since the material pressure in the inner cylinder 2 is higher than the pressure in the annular channel 6. In order to reduce the pressure difference to which the outer separator 107 is subjected, the process shown in fig. 3 is adopted, and the reaction apparatus in the process maintains the stable reaction temperature by absorbing the reaction heat by using the high-flow circulation flow of the high-boiling-point reaction raw material chlorinated aromatic hydrocarbon in the annular space channel 6. The concurrent heat exchange is preferably used to minimize the pressure differential experienced by the outer diaphragm 107 and to harness the exothermic heat of reaction through an external heat exchanger system. In addition, the design scheme that a plurality of plug flow reaction devices of the same type are connected in series can be adopted to meet the productivity requirement, each plug flow reaction device adopts spiral channels with different section sizes according to different gas-liquid flow loads, the working condition of the spiral channels in each plug flow reaction device is optimized, and the problem that the plug flow reaction device is difficult to transport from a road due to the fact that the size and the weight of the plug flow reaction device exceed the standard is avoided. Meanwhile, sleeve heat exchange is arranged on a material flow pipeline between the series plug flow reaction devices to optimize temperature control. The material outlet pipe at the top of each plug flow reaction device is respectively provided with a safety pressure relief control device, so that the internal pressure of the plug flow reaction device can be reduced rapidly and controllably when an accident occurs, and materials in the plug flow reaction device are discharged to the accident storage tank condensation collection system for processing. And meanwhile, an emergency discharging pipeline is also designed on a material inlet pipe at the bottom of each plug flow reaction device, and a high-pressure-resistant double-pipe heat exchanger is arranged on the material inlet pipe for heat exchange, so that the material can be cooled firstly and then discharged to an accident storage tank under high pressure, and the risk of accident treatment is reduced. And a spare pipeline and a valve are arranged for the series-connected plug flow reaction devices, so that the faulty plug flow reaction devices can be isolated and treated independently, and the rest plug flow reaction devices can still continue to run in series, thereby reducing the accident treatment cost.

As some embodiments of the application, the above-mentioned plug flow reaction device can be used, and the design of the process flow shown in fig. 4 is combined, so that the above-mentioned plug flow reaction device is suitable for producing phenyl or aryl chlorosilane by using benzene or arene and hydrogen-containing chlorosilane as raw materials and boron trifluoride or boron trichloride as a catalyst through catalytic dehydrogenation reaction, and because the reaction speed of the high-pressure gas-liquid phase is very slow and the reaction is weak in endothermic reaction, the high-flow circulation can be carried out in the annular gap channel 6 of the plug flow reaction device by adopting the raw material benzene or arene with higher boiling point to carry heat, and the heat required by the reaction is provided for the reactant through the heat conduction of the side wall of the inner cylinder 2.

In fact, although boron trifluoride catalysis can effectively reduce the reaction temperature, because boron trifluoride has a very low boiling point and hydrogen which is difficult to condense is generated in the reaction, the catalyst is easy to carry away by hydrogen, and the contact between the catalyst and reactants is difficult to be maintained for a long time with low cost in a common method, so that the process for producing phenylchlorosilane by using boron trifluoride catalysis has not been reported to be used in the production process.

However, in the application, by adopting the ultra-long horizontal spiral flow channel as the main body of the reaction zone, for a small-capacity plug flow type reaction device, a rectangular flow channel section with the height smaller than the width can be adopted to enable a high-pressure reaction gas-liquid mixture to be continuously turned and sucked in a turning way in the flowing process to form continuous turbulent flow mixing, for a large-capacity plug flow type reaction device, a square-section horizontal spiral flow channel is adopted, and a shaftless auger screw is arranged in the horizontal spiral flow channel to bring about enhanced mixing effect, so that the problem of separation of reactants and catalysts is avoided, the boron trifluoride catalyst with the very low boiling point can be normally used, the catalytic effect is better than that of boron trichloride, and the high-efficiency mixing and mass transfer capability is favorable for avoiding adopting high reaction temperature, thereby improving the reaction selectivity. In addition, the process flow of fig. 4 also realizes the recycling of boron trifluoride catalyst with low cost.

In addition, in order to suppress vibration damage caused by mixed gas-liquid flow, a complicated reinforcing and fixing measure is generally required to be constructed, and when a large-scale high-pressure production device for such a slow reaction is constructed by adopting a tubular reactor, high safety and guaranteeing costs are required because hundreds of tons of high-temperature high-pressure dangerous materials are kept to be contained in the operation of the reactor system. The spiral channel reaction main body structure arranged in the plug flow type reaction device provided by the invention has good rigidity, and can effectively avoid severe vibration caused by gas-liquid mixed flow, so that the safety guarantee cost is greatly reduced.

Moreover, in general, the high-pressure liquid-phase condensation process and the catalytic dehydrogenation process for producing the aryl chlorosilane can generate gases which are difficult to condense in the reaction process, and the gas-liquid mixed flow working condition cannot be avoided. The condensation method and the catalytic dehydrogenation method have the advantages of complementation, and can be used for constructing a large-scale phenylchlorosilane production device in a matched manner, so that the best economic benefit can be obtained.

For example, 5 plug flow type reaction devices with the outer diameter of 2000mm and the weight of 220 tons/table and the design pressure of 18MPa are connected in series to construct a system for synthesizing phenyl chlorosilane by a high-pressure liquid-phase condensation method with the capacity of 2 ten thousand tons/year, and the byproduct phenyl hydrogen-containing dichlorosilane with the capacity of 6000 tons/year can be used for producing other special phenyl chlorosilanes such as vinyl phenyl dichlorosilane. However, at the same time, the system can also produce a large amount of benzene containing trace chlorosilane, and the byproduct benzene is difficult to be accepted by the market and is difficult to treat, but is very suitable for being used as a raw material for synthesizing phenylchlorosilane by a catalytic dehydrogenation process. Correspondingly, 5 plug flow type reaction devices with the outer diameter of 2800mm and the weight of 280 tons/table and the design pressure of 12MPa are connected in series, and a catalytic dehydrogenation method phenyl chlorosilane synthesis system with the capacity of 5 ten thousand tons/year is built, which can mainly produce the methyl phenyl dichlorosilane when the low-purity monomethyl hydrogen-containing dichlorosilane is used as a raw material, or mainly produce the diphenyl dichlorosilane when the low-purity dichlorosilane by-produced by a silicon tetrachloride cold hydrogenation device is used as a raw material. The combined process can utilize benzene as a byproduct, and realize large-scale low-cost clean production of various phenylchlorosilanes with the largest market demand. It should be noted that: the pressure and temperature of the reactor used in the catalytic dehydrogenation method are much lower than those in the high-pressure liquid-phase condensation method, so that the catalytic dehydrogenation method can adopt an outer cylinder body 3 with a thinner wall thickness to reduce the weight, the outer cylinder body 3 can be used for preparing a stainless steel/carbon steel composite cylinder body by using a low-cost explosion compounding method, and the manufacturing cost can be reduced by manufacturing an inner cylinder body 2 component by using cheaper stainless steel, such as 304L, so that the process is more suitable for a device with high productivity.

As further embodiments of the present application, as shown in fig. 5, the spiral channel in the reaction unit 1 is implemented with concentric multi-layer loops 10 having equal width intervals, a blind plate 11 is disposed on the vertical surface of each concentric loop in the concentric multi-layer loops 10, the same concentric loop is divided into non-connected circular loops by the blind plate 11, and a communication port 12 is disposed at one side of the blind plate 11, the communication port 12 communicates with adjacent inner and outer circular loops, so that the spiral channel is in a spiral shape as a whole, and the reaction fluid can sequentially flow through each layer of concentric loops through the communication port 12, and gradually flow toward the inner layer of the concentric multi-layer loops 10 or flow toward the outer layer. At this time, the reaction unit inlets 103 and the reaction unit outlets 104 of the reaction units 1 adjacent to each other are respectively at the blind plate 11 of the outermost circular channel or at the center of the innermost circular channel, so that the channels of the two adjacent circular channels are connected in series.

Further, the positions of the blind plates 11 and the communication ports 12 can be adjusted so that the reactant fluids in the adjacent inner and outer circular paths flow in the same or opposite directions. Preferably, the positions of the blind plates 11 and the communication ports 12 are adjusted so that the reactant fluids in the adjacent inner-layer circular paths and the outer-layer circular paths flow in opposite directions, and the fluids in the adjacent circular paths can realize countercurrent heat exchange through the wall surfaces to reduce the reaction temperature difference.

The horizontal plug flow type reaction device provided with the concentric multi-layer annular channel 10 can also use a rolling bending machine to process rectangular pipes to construct horizontal spiral channel units to reduce the construction difficulty for reactors with small productivity, and for reactors with large productivity, the thin steel plates are cut and fed and processed into single-ring channel units with batch multi-series and standardized structures, then the single-ring channel units of different series are subjected to cross stacking assembly welding to construct the structure of the inner cylinder body 2 in the horizontal plug flow type reaction device, and the processing method is convenient for installing shaftless spiral augers in the horizontal annular flow channels to optimize the mixed mass transfer of reaction fluids, so that the operation reliability of the reactors with large productivity is enhanced.

The structure of the plug flow type reaction device has modularized characteristics, so that the inner cylinder body 2 assembly and the outer cylinder body 3 assembly can be manufactured in an independent and sectional mode, the manufacturing efficiency is improved conveniently, and then the device is transported to a chemical plant site for assembly welding and assembly, so that the difficult problems of transportation and hoisting of a large-scale overweight reactor can be avoided, and the device can be used for building devices with the capacity of more than 10 ten thousand tons per year.

As still other embodiments of the present application, the present application also discloses a method for constructing a plug flow type reaction device, which has the advantage of being applicable to the production of products containing phenyl or aryl chlorosilanes with smaller capacity requirements, such as ethyl phenyl dichlorosilane and methyl chlorophenyl dichlorosilane for the production of special lubricating oil. The plug flow type reaction device in this embodiment adopts a small diameter circular tube or a small cross section square tube to manufacture a spiral channel, the capability of the inner pressure resistance and the outer pressure resistance of the pipeline is strong, the inner cylinder 2 can be prevented from being adopted to protect the pipeline, standard stainless steel tube straight tubes with the same specification are adopted to carry out bending processing to obtain a positive spiral channel 101 and a reverse spiral channel 102 of the reaction unit 1, then the two spiral channels are tightly crossed and arranged in the same plane through an assembly die and a fixed die, and then sealing welding structure construction is carried out at two ends, so that the ultra-long spiral channel similar to the flow is obtained. The construction method ensures that the outer side wall of the spiral channel is contacted with the inner wall of the outer cylinder body 3 of the reactor and welded to form reliable fixation, thus the structure of an annular gap channel 6 of the plug flow type reaction device manufactured by the former method is eliminated, but a communicated gap network is arranged between the spiral channels to realize the heat exchange function, for example, the reaction temperature can be controlled by selecting proper materials to carry out vaporization heat absorption or condensation heat release in the gap space network according to the reaction temperature and pressure, one of the reaction materials can be selected as the materials for heat exchange preferentially, other safe materials which can be compatible with the mixture of the reaction materials can be selected, and the specific selection standard of the heat exchange materials is to minimize the pressure difference of the wall of the spiral channel and the temperature difference of the reaction temperature, thereby being beneficial to the stability of the reaction temperature. Correspondingly, a differential pressure limiting safety protection system is also required to be arranged in the process flow adopted by the preparation method of the plug flow type reaction device, so that the spiral channel is prevented from being damaged. The plug flow type reaction device built by the method has the advantages of minimum welding workload, higher internal space utilization rate, and capability of reducing the number of reactors connected in series, but the requirements of the device on pipe quality and welding quality are improved.

In addition, the application also provides a plug flow type reaction device for the high-pressure reaction process, and the plug flow type reaction device is prepared according to the construction method.

The leakage-free high-pressure pump with high safety performance, such as a hydraulic metal diaphragm pump, can meet the requirement that the reaction raw materials of a continuous safe pumping high-pressure process enter a high-pressure reactor system, realizes the high-efficiency welding of the low-cost laser welding process on the thin-wall metal materials in China, solves the difficult problem of cutting and blanking the metal plate with complex shape by using numerical control laser cutting, realizes the large-scale high-precision Archimedes equal-pitch spiral forming process by using a novel numerical control rolling bender, also realizes the build-up welding composite process to reduce the manufacturing cost of a large-scale hydrogenation reactor with high temperature and high pressure in hydrogen and can assemble and weld the oversized reactor on site, so that the cost of developing a novel plug flow reactor for continuously producing the aryl chlorosilane by using the high-pressure liquid-phase reaction process can be greatly reduced, provides basic technical support for the construction of the plug flow reactor, and is easy to realize.

In summary, it can be seen that the plug flow type reaction device for the high pressure reaction process and the construction method thereof according to the present application have the following advantages:

Firstly, the reaction unit 1 designs a horizontal flow spiral channel with a compact structure as a reaction zone main body by an Archimedean spiral, equidistant spiral principle and equidistant concentric circle principle, and a shaftless auger belt can be arranged in the horizontal flow spiral channel to realize a plug flow reaction function of maintaining gas-liquid mixed flow, thereby being very beneficial to improving the reaction selectivity and conversion rate of high-pressure liquid phase synthesis of aryl chlorosilane;

secondly, the plug flow type reaction device uses the thin metal wall as a main body to construct a spiral channel for horizontally flowing reactants by mixing high-pressure gas and liquid phases, so that the spiral channel is easy to process with high efficiency, and the manufacturing cost of the device can be greatly reduced;

thirdly, the plug flow type reaction device has good structural anti-seismic performance, can ensure long-term operation safety, can replace a high-temperature gas condensation method to realize a large-capacity production device, and meets the requirements of environmental protection in the process, improvement of product quality and reduction of production cost;

fourthly, the plug flow type reaction device adopts a specific process flow to ensure the safety of the internal structure of the reactor;

fifthly, the plug flow reaction device can realize the efficient boron trifluoride catalytic dehydrogenation process to produce the aryl chlorosilane so as to improve the economy, and the process flow enables the catalyst to be easily separated and can realize the recycling of the catalyst;

Sixth, the plug flow type reaction device can adopt two processes of a high-pressure liquid phase non-catalytic condensation method and a catalytic dehydrogenation method, and a large-scale phenylchlorosilane production device is built in a combined mode to improve economy;

seventh, the plug flow reaction device and the construction method thereof can avoid using expensive metal materials, greatly reduce the use amount of the metal materials, greatly reduce the construction cost of the reaction device for producing the phenylchlorosilane by using the hydrogen-containing chlorosilane in high-pressure liquid phase reaction, eliminate the high-temperature gas condensation method and the direct method which have poor product quality, pollute and high cost to produce the phenylchlorosilane, realize the clean production with large productivity and low cost, and are beneficial to expanding the product types and improving the economic benefit.

The embodiments of the present application have been described above with reference to the accompanying drawings, in which the embodiments of the present application and features of the embodiments may be combined with each other without conflict, the present application is not limited to the above-described embodiments, which are merely illustrative, not restrictive, of the present application, and many forms may be made by those of ordinary skill in the art without departing from the spirit of the present application and the scope of the claims, which are protected by the present application.

Claims

1. A method of constructing a plug flow reaction apparatus for a high pressure reaction process, the plug flow reaction apparatus comprising:

at least one reaction unit (1), the reaction unit (1) having a reaction unit inlet (103) and a reaction unit outlet (104);

the reaction unit (1) is provided with a spiral channel which is spiral in the horizontal direction, reaction materials enter the spiral channel through the inlet (103) of the reaction unit, and are discharged through the outlet (104) of the reaction unit after carrying out plug flow reaction in the spiral channel.

2. The method of constructing a plug flow type reaction apparatus according to claim 1, wherein the spiral channel is a spiral reaction channel extending along archimedean spiral or equidistant spiral.

3. The method of constructing a plug flow reaction device according to claim 1, wherein the spiral channel comprises:

the device comprises equally-spaced concentric multi-layer annular channels (10), wherein blind plates (11) are arranged on the vertical surfaces of all the concentric annular channels in the concentric multi-layer annular channels (10), the same concentric annular channel is divided into non-communicated circular annular channels through the blind plates (11), one side of each blind plate (11) is provided with a communication port (12), and the communication ports (12) are communicated with adjacent inner-layer annular channels and outer-layer annular channels;

The reaction fluid sequentially flows through all layers of concentric circular loops through the communication ports (12) and flows to the inner layer of the concentric circular multi-layer loop (10) or flows to the outer layer;

4. A method of constructing a plug flow reaction apparatus according to claim 1, 2 or 3, wherein the helical channels are manufactured by bending straight pipes of circular or square cross section.

5. The method of constructing a plug flow reaction device according to claim 2, wherein the reaction unit (1) comprises:

two spiral channels arranged side by side, wherein one of the spiral channels is marked as a positive spiral channel (101), the other one is marked as a negative spiral channel (102), the positive spiral channel (101) and the negative spiral channel (102) are mutually communicated, and the flowing directions of reaction materials in the positive spiral channel (101) and the negative spiral channel (102) are opposite;

the reaction material enters the reaction unit (1) through the reaction unit inlet (103), flows through the positive spiral channel (101) and the reverse spiral channel (102) in sequence for reaction, and is discharged through the reaction unit outlet (104).

6. The method of constructing a plug flow reaction apparatus according to claim 5, wherein the cross sections of the forward spiral channel (101) and the reverse spiral channel (102) are rectangular cross sections having a width dimension larger than a height dimension.

7. The method of constructing a plug flow reaction device according to claim 1, further comprising:

an inner cylinder (2) arranged in the vertical direction;

an outer cylinder (3) which is arranged around the periphery of the inner cylinder (2);

an annular gap between the inner cylinder body (2) and the outer cylinder body (3) forms an annular gap channel (6), and a temperature control medium flows in the annular gap channel (6) to regulate and control the temperature of the reaction unit (1);

8. The method of constructing a plug flow reaction device according to claim 7, further comprising:

the upper end socket and the lower end socket are oppositely arranged at two ends of the inner cylinder body (2);

9. The method for constructing a plug flow type reaction apparatus according to claim 7, wherein,

the inner cylinder body (2) is prepared from 316L or 304L stainless steel;

the outer cylinder body (3) is prepared from hydrogen embrittlement resistant carbon steel containing chromium and molybdenum elements, and stainless steel 321 or 309 is deposited on the inner wall of the outer cylinder body; or the outer cylinder (3) is a stainless steel/carbon steel composite cylinder prepared by an explosion composite method.

10. The method of constructing a plug flow reaction device according to claim 2, wherein the reaction unit (1) comprises:

a spiral separator 106 spirally provided in the reaction unit 1, the spiral passage being formed by crimping the spiral separator 106, the spiral separator 106 located outside the reaction unit 1 being referred to as an outer separator 107 constituting an outer wall of the reaction unit 1;

wherein, the spiral baffle plate (106) positioned in the reaction unit (1) is made of a thin-wall stainless steel plate with the thickness of 1.5-3 mm;

the outer partition plate (107) is made of a plate with the thickness of more than 15mm, and the outer partition plate (107) is made of a thick carbon steel plate of double-sided composite stainless steel.

11. The method of constructing a plug flow reaction device according to claim 2, wherein the plug flow reaction device comprises:

The reactor comprises a plurality of reaction units (1), wherein the reaction units (1) are stacked along the vertical direction, and the reaction units (1) are sequentially connected in series through a reaction unit inlet (103) and a reaction unit outlet (104) to form a reaction zone main body of the plug flow type reaction device.

12. A plug flow reaction device, characterized in that the plug flow reaction device is prepared by the construction method according to any one of claims 1 to 11.