CN114505022B - Impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene - Google Patents
Impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene Download PDFInfo
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 28
- UAZUEJTXWAXSMA-UHFFFAOYSA-N 1,1-dichlorobut-1-ene Chemical compound CCC=C(Cl)Cl UAZUEJTXWAXSMA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000012495 reaction gas Substances 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims 6
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 8
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FQDIANVAWVHZIR-UPHRSURJSA-N (z)-1,4-dichlorobut-2-ene Chemical class ClC\C=C/CCl FQDIANVAWVHZIR-UPHRSURJSA-N 0.000 description 1
- XVEASTGLHPVZNA-UHFFFAOYSA-N 3,4-dichlorobut-1-ene Chemical class ClCC(Cl)C=C XVEASTGLHPVZNA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical class ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene, which comprises a reactor in a high-temperature state and a premixer in a normal-temperature state. The reactor is provided with a reaction cylinder, the side surface of the upper end part of the reaction cylinder is provided with a reaction gas inlet, the bottom end of the reaction cylinder is provided with a reaction gas outlet, the upper end part of the interior is a entrainment zone, and the lower end part of the interior is a pipe flow zone; the premixer comprises a main pipe and a side pipe arranged at the side end of the main pipe along the axis of the main pipe; two ends of the main pipe are respectively used as an ethylene feed inlet and a mixed gas discharge outlet, a plurality of rows of first small holes and second small holes which are staggered are arranged at the overlapping part of the side surface and the side pipe, the axes of the first small holes and the main pipe form a certain angle, and the second small holes are vertical to the main pipe; the feed inlet of the side pipe is taken as a chlorine feed inlet and is vertical to the ethylene feed inlet. The pre-mixer is specially designed, so that the mixing time is short, and the mixing effect is good; the reactor has the advantages of large entrainment back mixing amount, rapid inlet gas mixing, uniform temperature distribution and reasonable reaction residence time distribution.
Description
Technical Field
The invention belongs to the technical field of dichlorobutene preparation, and particularly relates to an impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene.
Background
The chloroprene rubber is synthesized by polymerizing, monomer removing, condensing and drying chloroprene (2-chloro-1, 3-butadiene) monomer, and has excellent illumination resistance, aging resistance, deflection resistance, acid and alkali resistance, ozone resistance, combustion resistance, heat resistance and oil resistance, and good physical and mechanical properties and electrical properties. The preparation of chloroprene monomer mainly comprises two methods of acetylene method and butadiene method, wherein the process for preparing chloroprene by butadiene gas-phase chlorination method has the advantages of low raw material cost, good production safety, high monomer quality, comprehensive utilization of byproducts and the like, and is widely paid attention to.
The method for preparing chloroprene monomers by the butadiene gas-phase chlorination method can be divided into the following three steps: chlorination, isomerization and dehydrochlorination, where chlorination is the most important step. In the chlorination section of butadiene, the butadiene and chlorine react at 280-330 ℃ in an addition reaction mode, the reaction is an irreversible exothermic reaction, the reaction speed is extremely high, the heat release amount is large, the generated target product is dichlorobutene, and the target product comprises three isomers of 3, 4-dichloro-1-butene, cis-1, 4-dichloro-2-butene and trans-1, 4-dichloro-2-butene, and byproducts comprise low-boiling-point substances such as chloroprene and high-boiling-point substances such as polychloride and tar. To avoid further chlorination of the dichlorobutene, an excess of butadiene is generally added to increase the selectivity of the reaction, the molar ratio of butadiene to chlorine being 3 to 10.
In order to increase the selectivity of the reaction, the mixing and heat exchange efficiency of the reactor need to be considered simultaneously. In early researches, the inlet part of the reactor adopts a double-nozzle structure, and the main part adopts a one-stage adiabatic reactor; considering that high Wen Xiading diene can polymerize, the raw material gas is introduced at normal temperature, and the inlet gas and high-temperature gas in the reactor are mixed in a entrainment and back mixing way, so that the temperature is quickly raised to a temperature suitable for reaction. For different process conditions, a two-stage adiabatic reactor can be used instead, and a second stage is added to ensure the residence time of the reaction gas. Under the process conditions, the equipment can continuously operate, and the yield of the dichlorobutene is kept above 90 percent. However, this reactor structure has the following problems:
1. butadiene and chlorine are single-point feeding, and a high-concentration area of chlorine is inevitably generated at the reaction temperature, so that the reaction yield is affected, and high-boiling-point chloride is generated to block the gas feeding, so that long-time production cannot be ensured;
2. the nozzle for reaction is positioned above the reactor, the inlet axis is coincident with the axis of the reactor and the outlet axis, and the structure can lead part of feed to directly leave the reactor without mixing, so that the residence time is very uneven, and the conversion rate of the reaction is affected;
3. the entrainment back mixing effect generated by a single nozzle is poor, the proportion of the back mixing amount to the feeding amount is low, the effect of rapid temperature rise cannot be achieved, and the conversion rate and the selectivity of the reaction are affected.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, and the solution to the above-mentioned drawbacks is as follows:
(1) Providing a device for rapidly mixing two raw materials, uniformly mixing the raw materials in a very short time, eliminating a high-concentration area of chlorine and improving the reaction selectivity;
(2) Providing a proper reactor structure, increasing the entrainment back mixing amount of the entrainment region and leading the temperature distribution to be more uniform;
(3) A proper reactor structure is provided, the minimum residence time is ensured, the residence time distribution is made to be as uniform as possible, and the reaction conversion rate is improved.
Accordingly, the invention provides an impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene, which comprises the following specific technical scheme:
the impinging stream reactor for preparing the dichlorobutene by the gas-phase chlorination of the butadiene provided by the invention comprises a reactor in a high-temperature state and a premixer in a normal-temperature state.
The reactor is provided with a reaction cylinder, the side surface of the upper end part of the reaction cylinder is provided with a reaction gas inlet, the bottom end of the reaction cylinder is provided with a reaction gas outlet, the upper end part of the interior of the reaction cylinder is a entrainment zone, and the lower end part of the interior of the reaction cylinder is a pipe flow zone;
the premixer comprises a main pipe and a side pipe arranged at the side end of the main pipe along the axis of the main pipe; two ends of the main pipe are respectively used as an ethylene feed inlet and a mixed gas discharge outlet, a plurality of rows of first small holes and second small holes which are staggered are arranged at the overlapping part of the side surface and the side pipe, the axes of the first small holes and the main pipe form a certain angle, and the second small holes are vertical to the main pipe; the feed inlet of the side pipe is taken as a chlorine feed inlet and is vertical to the ethylene feed inlet.
In the invention, the entrainment region in the reaction cylinder refers to a region where the mixed reaction gas is injected into the reactor from an inlet at high speed and is impacted on a symmetrical surface to generate entrainment and vortex, and the normal temperature gas entering in the region is rapidly mixed with the high temperature gas in the reactor to reach a temperature suitable for reaction and react; the pipe flow area refers to an area in which gas flows along the axial direction to the outlet after leaving the entrainment area and the whole is approximately in plug flow movement, and the reaction gas leaves the reactor through the reaction gas discharge port after continuing to react for a period of time.
Further, in the impinging stream reactor provided by the invention, the reaction cylinder body consists of a cylindrical cylinder body, an upper sealing head and a lower sealing head. The upper end enclosure is provided with a manhole, the lower end enclosure is provided with a reaction gas outlet, and the reaction gas inlet is vertically and symmetrically arranged at the side end of the upper end part of the cylindrical barrel.
Further, in the impinging stream reactor provided by the invention, the gas inlet speed of the reaction gas inlet is 100-200 m/s, and the internal reaction temperature is 280-330 ℃.
Further, in the impinging stream reactor provided by the invention, the ratio of the length to the diameter of the reaction cylinder is 2-20, and the ratio of the diameter of the reaction cylinder to the diameter of the reaction gas inlet is 5-50.
Further, in the impinging stream reactor provided by the invention, the ratio of the distance from the reaction gas inlet to the upper end of the reaction cylinder to the diameter of the reaction cylinder is 0.5-1.
Further, in the impinging stream reactor provided by the invention, the first orifice and the second orifice have the same diameter. The vertical distance between the first small holes and the second small holes is 2-10 times of the diameter of the small holes, the number of the first small holes or the second small holes in each row of small holes is 4-8, and the included angle between the axis of the first small holes and the normal line of the main pipe is 15-30 degrees.
Further, in the impinging stream reactor provided by the invention, the ratio of the length of the main pipe to the diameter is 5-100, and the ratio of the diameter of the main pipe to the diameter of the first small hole or the second small hole is 5-20.
Further, in the impinging stream reactor provided by the invention, the average residence time of the mixture stream in the premixer is 0.001 to 0.01 seconds, and the average residence time of the reactant stream in the reactor is 4 to 10 seconds.
Effects and effects of the invention
Compared with the structure and the reaction mode of the existing gas-phase chlorination reactor, the invention has the following technical advantages:
(1) According to the invention, a method of premixing at normal temperature and then entering a reactor for heating reaction is adopted, butadiene and chlorine are mixed rapidly in advance at normal temperature, so that side reaction generated during mixing at high temperature is fundamentally prevented, meanwhile, self-polymerization of high Wen Xiading diene is avoided, mixed raw material gas is injected into the reactor at high speed to generate impact and entrainment reflux, and the mixed raw material gas is mixed rapidly with original gas in the reactor for heating to reach reaction temperature, and meanwhile, heat released by reaction is absorbed, so that additional heat exchange equipment is avoided;
(2) The pre-mixer adopts a tubular mixer, a plurality of rows of small holes are arranged on the side surface, a certain angle exists between the axis of a front row of first small holes and a main pipe, a rear row of second small holes are perpendicular to the main pipe, the first small holes and the second small holes are alternately arranged in a perforating mode, the pore diameters of the front row and the rear row are mutually staggered or are consistent in the front-rear direction, and the pre-mixer is characterized in that a side surface spraying mode of alternately combining rotary jet flow and vertical jet flow is used. The advantage of this is that the separate rotating jets are able to mix the two gases rapidly, but produce a concentration difference in the radial direction; the back row of small holes is changed into a vertical jet flow, so that a regular flow field formed by the rotating jet flow can be changed, and an alternating mode of rotating the jet flow firstly, then rotating the jet flow vertically is formed, and the mixing is faster and more effective.
(3) The invention uses the opposed feed inlets, the two feed inlets are oppositely arranged on the side surface of the upper end part of the reactor, so that two mixed gases enter the reactor to collide on a symmetrical surface, the interior of the reactor is divided into a entrainment region and a pipe flow region according to a flow field formed by the collision, wherein the entrainment region refers to a severe entrainment back mixing region formed by the collision, and in the region, the inlet normal-temperature gas can be quickly mixed with high-temperature gas in the reactor to raise the temperature and absorb heat released by the reaction; the pipe flow area refers to the area that after leaving the entrainment area, the gas flows along the axial direction to the outlet, and in the area, the gas is not mixed any more, and the whole is approximately in plug flow movement, so that the minimum residence time of the reaction gas is effectively ensured.
In conclusion, the premixer for preparing the dichlorobutene by gas-phase chlorination of butadiene is a side injection premixer with special design, has short mixing time and good mixing effect; meanwhile, the reactor has a simple structure, and is suitable for rapid mixing of butadiene and chlorine and is also suitable for mixing of other gases.
In addition, the opposed reactor for preparing the dichlorobutene by the gas-phase chlorination of the butadiene has the characteristics of large entrainment back mixing amount, rapid inlet gas mixing, uniform temperature distribution, reasonable reaction residence time distribution, high reaction conversion rate and selectivity and the like, is suitable for the reaction of the butadiene and the chlorine, and is also suitable for other exothermic gas-phase reactions.
Drawings
FIG. 1 is a schematic view of the structure of a premixer of the present invention.
FIG. 2 is a schematic diagram of the open holes of sections A-A and B-B in FIG. 1.
FIG. 3 is a schematic structural view of the reactor of the present invention.
In the figure: 1-main pipe inlet, 2-pre-mixer main pipe, 3-pre-mixer side pipe, 4-side pipe inlet, 5-first small hole, 6-second small hole, 7-main pipe outlet, 8-reaction gas inlet, 9-reactor entrainment zone, 10-reactor pipe flow zone, 11-reaction gas outlet, 12-manhole, 13-upper end enclosure, 14-cylindrical barrel and 15-lower end enclosure.
Detailed Description
The present invention will be described in detail with reference to the following examples and the accompanying drawings. The following examples should not be construed as limiting the scope of the invention.
Example 1
According to fig. 1 and 3, the impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene provided in this embodiment comprises a premixer 100 at normal temperature and a reactor 200 at high temperature.
According to fig. 1, the premixer 100 includes a main pipe 2 and a side pipe 3 provided at a side end of the main pipe along a main pipe axis; two ends of the main pipe 2 are respectively provided with a main pipe inlet 1 serving as an ethylene feed inlet and a main pipe outlet 7 serving as a mixed gas discharge outlet, and a plurality of rows of first small holes 5 and second small holes 6 with the same diameter are arranged at the overlapping position of the side surface and the side pipe.
According to fig. 1 and 2, the ratio of the length L1 of the main pipe to the diameter D1 is 5 to 100, and the ratio of the main pipe diameter D1 to the diameter D1 of the first small hole or the second small hole is 5 to 20. The premixer holes are divided into a plurality of rows, the number of the first holes or the second holes in each row is 4-8, and the vertical distance h1 between the holes in each row is 2-10 times of the diameter d1 of the holes. The included angle alpha between the axis of the first small hole 5 and the normal line of the main pipe is 15-30 degrees, and the second small hole 6 is vertical to the main pipe. The first small holes 5 and the second small holes 6 of each row are alternately arranged in a hole forming mode, and the pore diameters of the front row and the back row are staggered or consistent. The main pipe outlet 7 is directly connected with the reaction gas inlet 8.
The feed inlet 4 of the side pipe 3 is used as a chlorine feed inlet and is perpendicular to the ethylene feed inlet. When butadiene and chlorine are mixed, the butadiene flows into the main pipe 2 through the main pipe inlet 1, the chlorine enters the side pipe 3 through the side pipe inlet 4, then is injected into the main pipe 2 from the small holes to be mixed with the butadiene, the average residence time of the mixture flow is 0.001-0.01 seconds, and the mixture flow is directly discharged from the main pipe outlet 7 into the reactor after being mixed.
According to fig. 3, the reactor 200 has a reaction cylinder composed of an upper head 13, a cylindrical cylinder 14, and a lower head 15 in this order from top to bottom, the upper head 13 and the lower head 15 being circular or elliptical heads. The side surface of the reaction cylinder is provided with a vertically symmetrical reaction gas feed inlet 8, a reaction gas outlet 11 is arranged below the reaction cylinder, and a manhole 12 is arranged above the reaction cylinder; the upper part of the interior is a entrainment zone 9 and the lower part is a tube flow zone 10.
In this example, the ratio between the reactor length L2 and the diameter D2 is 2 to 20; the ratio between the reactor diameter D2 and the reaction gas feed port diameter D2 is 5 to 50. The ratio of the distance H2 of the reaction gas feed inlet from the upper end of the reactor to the diameter D2 of the reactor is 0.5-1.
When the reaction is carried out, the gas inlet speed of the premixed reaction gas at the position of the reaction gas outlet 11 is 100-200 m/s, after the premixed reaction gas is injected into the reaction cylinder body at high speed, the premixed reaction gas is impacted on the symmetrical surface of the entrainment region 9 to generate entrainment and vortex, and the premixed reaction gas is rapidly mixed with high-temperature gas with the temperature of 280-330 ℃ in the reactor in the entrainment region 9 to reach a temperature suitable for the reaction and react. After the reaction gas leaves the entrainment zone 9, the gas flows axially towards the outlet in a pipe flow zone 10, the whole is approximately plug flow, and the reaction gas leaves the reactor through a reaction gas outlet 11 after continuing to react for a period of time. The average residence time of the reactant stream in the reactor is 4 to 10 seconds.
The reaction product is fed into the degassing tower after flowing out of the reactor from a reaction gas outlet at the bottom of the reactor, wherein unreacted butadiene is returned to the chlorination tower. The mixed dichlorobutene is discharged from the bottom of the degassing tower, and the heavy fraction is separated and then enters an isomerization reactor.
Specific application example
A device for preparing dichlorobutene by gas-phase chlorination of 1 ten thousand tons/year butadiene, wherein a reactor adopts an impinging stream reactor structure form for preparing dichlorobutene by gas-phase chlorination of butadiene as shown in figure 3,
560Nm of butadiene in main pipe feed 3 /(m 3 H), side tube feed chlorine 140Nm 3 /(m 3 H) the feeding temperature is 25 ℃, the length of a main pipe of the premixer is 330mm, the diameter of the main pipe is 35mm, the diameters of small holes are 7mm, four small holes in each row are distributed in a front-back consistent way, the included angle between the front small holes and the normal line of the main pipe is 20 DEG, the rear small holes are perpendicular to the main pipe, the vertical distance between the two small holes is 20mm, two gas inlets are arranged on two sides of the reactor, each inlet is connected with one premixer, the diameter of the inlet is the diameter of the main pipe, the total length of the reactor is 2850mm, the length of a cylinder is 2300mm, the diameter of the cylinder is 640mm, the inlet is 600mm from the top end of the reactor, the gas inlet speed is 100m/s, the average temperature inside the reactor is 300 ℃, the average residence time is 4 seconds, the chlorine conversion rate is 100%, the reaction yield of the dichlorobutene is 95%, and the yield reaches 1.02 ten thousand tons/year (in 8000 hours per year).
In summary, the continuous heat exchange impinging stream reactor for preparing the dichlorobutene by the gas-phase chlorination of the butadiene has the following advantages:
1. the method adopts the design of mixing at normal temperature and then introducing the mixture into a reactor for heating reaction, butadiene and chlorine are mixed in advance and rapidly at normal temperature, so that side reactions caused by mixing at high temperature are fundamentally prevented, meanwhile, self-polymerization of high Wen Xiading diene is avoided, mixed raw material gas is injected into the reactor at high speed to generate impact and entrainment reflux, and the mixed raw material gas is mixed with original gas in the reactor rapidly and heated to reach the reaction temperature, and meanwhile, heat released by the reaction is absorbed, so that additional heat exchange equipment is avoided;
2. the rotary jet flow and the vertical jet flow of the premixer are alternately combined, the front row of small holes adopts a rotary jet flow mode, and the rear row of small holes adopts a vertical jet flow mode, so that the mixing is faster and more effective;
3. by adopting the design of the opposite reaction gas inlets, the gas is injected into the reactor from the feed inlet at high speed, and is impacted on the symmetrical surface to generate entrainment and vortex, so that the process of mixing and heating can be greatly accelerated, the occurrence of side reactions is reduced, and the reaction selectivity is improved;
4. the inlet is arranged on the side surface of the reactor, so that the coincidence with the axis of the outlet is avoided, the minimum residence time of the reaction gas is ensured, and the conversion rate of the reaction is improved;
5. the reactor has simple integral structure, is easy to process, transport and assemble and disassemble, has variable height-diameter ratio, and is applicable to the chlorination reaction of butadiene under different process conditions and other exothermic gas phase reactions.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. An impinging stream reactor for the vapor phase chlorination of butadiene to make dichlorobutene comprising: a reactor in a high temperature state and a pre-mixer in a normal temperature state, wherein the average residence time of the mixture flow in the pre-mixer is 0.001-0.01 seconds, the average residence time of the reactant flow in the reactor is 4-10 seconds,
wherein the reactor is provided with a reaction cylinder body, the side surface of the upper end part of the reaction cylinder body is provided with a reaction gas inlet, the bottom end of the reaction cylinder body is provided with a reaction gas outlet, the upper end part of the interior of the reaction cylinder body is a entrainment zone, the lower end part of the interior of the reaction cylinder body is a pipe flow zone,
the premixer comprises a main pipe and a side pipe arranged at the side end of the main pipe along the main pipe axis; two ends of the main pipe are respectively used as a butadiene feed inlet and a mixed gas discharge outlet, a plurality of rows of first small holes and second small holes which are staggered are arranged at the overlapping part of the side surface and the side pipe, the axes of the first small holes and the main pipe form a certain angle, and the second small holes are vertical to the main pipe; the feed inlet of the side pipe is taken as a chlorine feed inlet and is vertical to the butadiene feed inlet,
and the mixed gas discharge port is connected with the reaction gas inlet.
2. The impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene according to claim 1, wherein:
the reaction cylinder consists of a cylindrical cylinder body, an upper end socket and a lower end socket, wherein a manhole is arranged on the upper end socket, a reaction gas outlet is arranged on the lower end socket, and a reaction gas inlet is vertically and symmetrically arranged at the side end of the upper end part of the cylindrical cylinder body.
3. The impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene according to claim 2, characterized in that:
wherein the gas inlet speed of the reaction gas inlet is 100-200 m/s, and the internal reaction temperature is 280-330 ℃.
4. The impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene according to claim 1, wherein:
wherein the ratio of the length to the diameter of the reaction cylinder is 2-20, and the ratio of the diameter of the reaction cylinder to the diameter of the reaction gas inlet is 5-50.
5. The impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene according to claim 1, wherein:
wherein the ratio of the distance from the reaction gas inlet to the upper end of the reaction cylinder to the diameter of the reaction cylinder is 0.5-1.
6. The impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene according to claim 1, wherein:
wherein the diameters of the first small hole and the second small hole are the same,
the vertical distance between the first small holes and the second small holes is 2-10 times of the diameter of the small holes, the number of the first small holes or the second small holes in each row of small holes is 4-8, and the included angle between the axis of the first small holes and the normal line of the main pipe is 15-30 degrees.
7. The impinging stream reactor for preparing dichlorobutene by gas-phase chlorination of butadiene according to claim 1, wherein:
wherein the ratio of the length to the diameter of the main pipe is 5-100, and the ratio of the diameter of the main pipe to the diameter of the first small hole or the second small hole is 5-20.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB914920A (en) * | 1960-09-17 | 1963-01-09 | Distillers Co Yeast Ltd | Production of dichlorbutenes |
| CN103007870A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Nozzle impinging stream rearrangement reactor |
| CN103962058A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Premixer, radial fixed-bed reactor and butaneoxidative dehydrogenation reaction system |
| CN203923239U (en) * | 2014-06-30 | 2014-11-05 | 陈维汉 | Coal gas and air grid premix spray the burner of many eddy current convolution preheated burnings |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB914920A (en) * | 1960-09-17 | 1963-01-09 | Distillers Co Yeast Ltd | Production of dichlorbutenes |
| CN103007870A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Nozzle impinging stream rearrangement reactor |
| CN103962058A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Premixer, radial fixed-bed reactor and butaneoxidative dehydrogenation reaction system |
| CN203923239U (en) * | 2014-06-30 | 2014-11-05 | 陈维汉 | Coal gas and air grid premix spray the burner of many eddy current convolution preheated burnings |
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