CN105776141B - A kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas - Google Patents
A kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas Download PDFInfo
- Publication number
- CN105776141B CN105776141B CN201610058441.6A CN201610058441A CN105776141B CN 105776141 B CN105776141 B CN 105776141B CN 201610058441 A CN201610058441 A CN 201610058441A CN 105776141 B CN105776141 B CN 105776141B
- Authority
- CN
- China
- Prior art keywords
- reactor
- catalyst
- pipe
- reactor shell
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The present invention relates to a kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, reactor shell is divided into multilayer in axial direction by supporting screening plate, catalyst is filled with every layer of sieve plate, every layer of catalytic inner is used to supply or remove inside reactor heat to ensure reaction temperature in claimed range equipped with multigroup heat exchanger tube, it is close to side-fed distributor is installed below sieve plate, ensure the catalytic activity of every layer of catalyst by adjusting side-fed amount, fixed below sieve plate and side-fed distributor by circular support circle, ensure that side-fed there are enough spatial mixings uniform.The reactor can effectively evenly remove heat caused by catalytic reaction, enhance heat, matter transmission efficiency, reduce flow resistance, reach good temperature control effect, and space reactor is made full use of reaction mass is farthest disperseed, more bed chargings extend the service life of catalyst, while reduce equipment investment, save production cost.
Description
Technical field
The invention belongs to technical field of chemical, and in particular to a kind of for the new of preparing chlorine by catalytic oxidation of hydrogen chloride
Type fixed bed reactors.
Background technology
Since Deacon (1886) catalytic oxidation of hydrogen chloride for preparing chlorine gas art inventions, around two big works of the technique
Cheng Wenti：Durability catalyst preparation and the design of high-performance reactor, always among constantly exploration and improvement.Wherein reactor
Aspect, because chlorination hydrogen catalysis oxygen process is strong exothermal reaction, reaction medium has very to reactor under the high temperature conditions in device
Severe corrosive, thus material to reactor and operating condition require harsher.In addition, effective removal of reaction heat and to anti-
The control of device temperature is answered, very high requirement also is proposed to the structure design of reactor.Therefore temperature of reactor control and equipment
The application of material is the key technology of catalytic oxidation of hydrogen chloride for preparing chlorine gas, but research and development so far in this regard are also much
Lag behind industrial actual demand.
It is fixed for the reactor fluidized-bed reactor and fixed bed reactors two types of preparing chlorine by oxidizing hydrogen chloride
Bed is big due to handling, low cost and operation is relatively easy and attention.
The shell and tube reactor for making catalyst using ruthenium-oxide of patent EP1894885A systems SUMITOMO CHEMICAL chemistry exploitation.Should
Reactor is designed for vertical row tubular type multistage heat transfer chamber, each heat transfer chamber not intercommunication, and the removal of fused salt heat-conducting medium is passed through in it
Heat caused by reaction, the control of each section of temperature of reactor is realized by the melting flow in each heat transfer chamber is adjusted, from
And realize the adjustment to whole temperature of reactor curve.Because the inducer reactant concentration of reactor is higher, reaction is more acute
Strong, temperature rise is very fast, and the activity of the higher ruthenium catalyst of the thermal conductivity loaded in tubulation will be segmented adjustment, the ruthenium content of catalyst
Ratio is adjusted from the 40% of reactor head to the bottom 100% of reactor, the pressure of whole reactor for 0.1~
1.0MPa, temperature are 200~500 DEG C.Although reaction bed temperature can be controlled and answered in satisfied degree, structure by the method
It is miscellaneous, involve great expense, operational control is cumbersome.More it is limited to difficulty of the active regulation of ruthenium catalyst in catalyst preparation.
Patent WO2013004651A1 describes the catalyst of cerium-carrying and ruthenium in the miniature isothermal reactor of bundled tube
The catalytic oxidation of hydrogen chloride application, proposition and patent EP1894885A very similar approach, are divided into 2~10 by bundled tube reactor
Conversion zone.With the catalyst of cerium-carrying in internal diameter 8mm, height 1000mm reactor, it is in feed rate ratio O2/HCl
0.75, reaction temperature≤420 DEG C, under conditions of 2~10bar of reaction pressure, the conversion ratio of hydrogen chloride has been carried out it is a series of not
With the experiment test of temperature of reactor section, it is believed that keep higher reaction temperature to be advantageous to improve hydrogen chloride for cerium catalyst
Conversion ratio.But the patent fails to provide the concrete structure and operating method of used isothermal reactor.
Patent CN102134057A proposes a kind of high temperature resistant, erosion resistant and corrosion resistant reactor, and outer protect is added on wall
Warm layer radiates to reduce, and inwall then adds, be anti-wear.But the reactor fails to do timely and effectively at heat transfer the heat of reaction generation
Reason, it is too high and inactivate to be easily caused catalyst local temperature.In addition, the patent does not penetrate into gold to reaction medium from inner liner
The secondary corrosion of category wall of reactor may further consider.
Based on case above, it is known that need a kind of more efficient preparing chlorine by oxidizing hydrogen chloride reactor, its have can and
When remove heat of reaction, control to adjust reaction temperature, and the advantage such as cheap, easy to use well.
The content of the invention
The technical problems to be solved by the invention, which are to provide one kind, can effectively remove exothermic heat of reaction, effectively control catalyst bed
Layer temperature, reduce catalyst bed layer resistance and space reactor can be made full use of to make the well mixed the catalytic oxidation of hydrogen chloride of material
Novel reactor.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of new fixation of catalytic oxidation of hydrogen chloride for preparing chlorine gas
Bed reactor, including reactor shell, upper cover, low head, multiple supporting screening plates, multiple side-fed distributors and multigroup use
In supply or remove inside reactor heat heat exchanger tube,
The reactor shell is vertically arranged, and the upper cover is provided with the top of the reactor shell, the installation of its bottom
There is the low head；Enterprising material mouth for being passed through unstrpped gas is installed on the upper cover, is provided with the low head
The lower discharge port of generation gas is reacted for discharging,
The supporting screening plate is horizontally fixed in the reactor cylinder body, and multiple supporting screening plates are along the reactor cylinder
The reactor shell is axially divided into multilayer by body, and catalyst, every layer of catalyst are filled with each sieve plate
Inside is provided with multigroup heat exchanger tube, and the heat exchanger tube is horizontally disposed in the catalyst, and multigroup heat exchanger tube is along described anti-
Device cylinder is answered axially to be evenly distributed in the catalyst；The side-fed distributor is horizontally fixed on the reactor shell
It is interior and positioned at identical with the supporting screening plate number and one by one close to the lower section of the supporting screening plate, the side-fed distributor
Corresponding, the bottom of the side-fed distributor is fixed with annular brace circle, the bracing ring and the reactor shell inwall
It is fixedly connected.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement：
Further, the heat exchanger tube is provided with the import for being used to be passed through heat transfer medium for being oppositely arranged on both sides and discharge passes
The outlet of thermal medium, the import and the outlet extend through the catalyst and stretched out on the outside of the reactor shell；Institute
State entrance and be provided with heat transfer medium imported valve, the imported valve in every layer of catalyst by after pipeline parallel connection by total
Valve controlling；The total valve of each layer is connected in parallel by pipeline.
Further, the heat exchanger tube is circular thermofin pipe, and the circular thermofin pipe includes being oppositely arranged on together
One plane and the first circular arc fin pipeline, the second circular arc fin pipeline and the multiple straight fins that are parallel to each other for being located at both sides
Pipeline, the straight fins pipeline are fixed between the first circular arc fin pipeline and the second circular arc fin pipeline；It is described
Size, the shape of first circular arc fin pipeline and the second circular arc fin pipeline are identical, the first circular arc fin pipeline,
It is interconnected between second circular arc fin pipeline and multiple straight fins pipelines, the one of the first circular arc fin pipeline
End be connected by the straight fins pipeline with the second circular arc fin pipeline, the first circular arc fin pipeline it is another
One end extends radially outward out composition and is passed through the import for moving thermal medium, and the import is through the catalyst and stretches out institute
State reactor shell；One end of the second circular arc fin pipeline passes through the straight fins pipeline and the first circular arc wing
Piece pipeline is connected, and the other end of the second circular arc fin pipeline extends radially outward out composition discharge heat transferring medium
The outlet, the outlet is through the catalyst and stretches out the reactor shell.
Further, circular thermofin pipe is staggered along reactor shell axial direction described in adjacent two groups, adjacent
Angle is 30~120 ° between circular thermofin pipe described in two groups；The internal diameter of the circular thermofin pipe is 25~100mm,
The distance between two neighboring described circular thermofin pipe is 50~1000mm.
Further, the side-fed distributor include main feed pipe and it is multiple be parallel to each other at grade it is straight
Pipe, described main feed pipe one end are provided with distributor charging aperture, other end sealing；The distributor charging aperture runs through the reactor
Cylinder is simultaneously protruding, and distributor charging aperture valve is provided with the distributor charging aperture；Multiple straight tubes are from the master
Charging the seal of tube one end rise uniformly is fixed on towards the other end on the main feed pipe, the straight tube it is closed at both ends, it is described
It is fixed in the middle part of straight tube on the main feed pipe and is connected with the main feed pipe；Plane where the straight tube with it is described anti-
Answer device cylinder cross section parallel；The straight tube bottom is provided with multiple equally distributed charging holes；The end of multiple straight tubes is equal
Be fixed on the top of the bracing ring, the bracing ring be fixed on the madial wall of Hu reactor shell；The side-fed
Distributor matches with the reactor shell inner shape.
Further, a diameter of 0.5~20mm of the charging hole；The internal diameter of the straight tube is 20~100mm, two neighboring
The distance between described straight tube is 50~500mm, and the length of the straight tube is 200~1800mm, the straight tube positioned at centre
Length it is most long, the straight tube gradually successively decreases from middle to both sides；The main feed bore is 20~100mm, and its length is
800~2200mm.
Further, heat tracing coil pipe is installed on the outside of the low head, the heat tracing coil pipe, which spirals, is welded on the low head
Outside, the heat tracing coil pipe disk are provided with heat tracing feed pipe inlet and heat tracing pipe outlet, are filled with the heat tracing coil pipe
Heat tracing medium；The internal diameter of the heat tracing coil pipe is 10~60mm.
Further, the supporting screening plate bottom margin is fixed on the inside of the reactor shell by multiple right angle pads,
While being fixed on the supporting screening plate bottom margin, its another side is fixed on the inside of the reactor shell right angle pad；
The supporting screening plate is circular hole punched holes type plate, and the aperture of the circular hole is 0.2~20mm.
Further, the supporting screening plate has 2~5, and the side-fed distributor has 2~5, and the heat exchanger tube has 6
~25 groups, the reactor shell is axially divided into 2~5 layers, described in every layer by the supporting screening plate along the reactor shell
Catalytic inner is provided with 2~5 groups of heat exchanger tubes, and the heat exchanger tube is horizontally disposed in the catalyst, heat exchange described in 2~5 groups
Pipe is axially evenly distributed in the catalyst along the reactor shell；The reactor shell internal diameter for 500mm~
2000mm, its axial height are 4500mm~18000mm；The height of the catalyst is 500mm~1500mm.
Further, the axial distance of the side-fed distributor and catalyst is 400~1000mm.
It is using the above-mentioned further beneficial effect of scheme:
1. the heat-transfer pipe in beds is welded to form by more parallel fins pipes with ring main, heat transfer medium is from ring
Shape house steward side enters, and is flowed out after flowing through each finned tube from opposite side ring main, and the parallel-connection structure feature of more finned tubes increases
The big heat transfer area of heat transfer medium；Likewise, heat-transfer pipe (is not limited to radially) finned tube using radial direction, can effective uniform conductive
Catalyst particle surface heat of reaction, improve heat transfer efficiency.
2. two layers adjacent of circular interlaced setting of thermofin pipe, the institute of two circular thermofin pipes
The angle for stating import formation is 30 °~120 DEG C, preferably 60~90 °, and beds radiating can be made more uniform, eliminated
Hot Biased flow phenomenon.
3. the input concentration that can control catalyst bed interlayer of feed distributor, makes material reaction more between catalyst layer
Fully, the conversion per pass of reactor is improved, and thermofin pipe can be coordinated to carry out auxiliary tune to the reaction temperature of reactor
It is whole.
4. the another effect that of feed distributor can rise sharply (industrial in catalyst bed reaction temperature between catalyst layer
Referred to as " temperature runaway ") in the case of, inert media (such as water vapour, nitrogen) is introduced into beds, effectively to suppress anti-
Device temperature is answered, prevents infringement of the excessive temperature to catalyst.
5. with the lengthening of catalyst usage time, its active component the continuous of gas phase flow media in reactor is washed away
It can assemble under effect to reactor exit, catalyst is used and equipment operation brings adverse effect.When catalyst inactivation shows
As going out when to reactor middle and lower part, this invention takes the method for upper and lower charging order commutation, i.e., by the bottom of reactor
Lower discharge port is as charging aperture, and the enterprising material mouth on reactor top is as discharging opening, and its side feed opening is according to catalyst inactivation
Situation is opened successively.
The present invention also has the advantages that：
(1) welding in parallel of the heat-transfer pipe with fin and ring main, compared with conventional one-channel spirals heat-transfer pipe, the biography
Heat pipe can effectively evenly remove heat caused by catalytic reaction, enhance heat, matter transmission efficiency, reduce flow resistance, radiating
In time uniformly, reach good temperature control effect, prevent hot-spot from causing catalyst inactivation or loss of active component.
(2) reactor of the invention is due to fin heat transfer pipe group, when reaction bed temperature is higher than heat-transfer medium temperature
Outwards to heat, when reaction bed temperature is less than heat-transfer medium temperature, from heat transfer medium by finned tube to beds
Heat supply, 250 DEG C of reactor temperature ＞ can be remained in the process of running, thus effectively prevent the generation of hot hydrochloric acid.
304 or 316L stainless steels thus can be used, compared with existing special nickelic or tantalum metal material reactor, equipment construction letter
Single, cost declines.The heat removed from coil pipe can be recycled as other thermals source, be effectively saved investment, reduce production
Cost.
(3) due to that long lasting for reaction the catalytic performance of catalyst can be caused constantly to reduce from top to bottom, multilayer is set
Charging aperture carries out multiple feed, and reactor inlet and outlet commutation charging, can make full use of catalyst, extend urge to greatest extent
Agent service life.
(4) side-fed distributor top is mounted directly sieve plate bottom installation bracing ring, utilizes distributor supporting screening plate, pole
The big distribution space for adding reaction mass, material is had the time mixing of abundance, improve reaction efficiency.Meanwhile it is distributed
Device and the two-in-one structure of sieve plate reduce one layer of bracing ring, have saved equipment investment compared with the two traditional separates.
(5) reactor can effectively prevent driving and parking or unusual service condition condition using heat tracing coil pipe is added on the outside of low head
The generation or accumulation of lower hydrochloric acid, the local corrosion of reactor is avoided, greatly prolong the service life of reactor.
In summary, the beneficial effects of the invention are as follows：The reactor effectively evenly removes heat caused by catalytic reaction,
Heat, matter transmission efficiency are enhanced, flow resistance is reduced, reaches good temperature control effect, and make full use of space reactor to make instead
Material is answered farthest to disperse, more bed chargings can extend the service life of catalyst, while reduce equipment investment, save
Production cost.
Brief description of the drawings
Fig. 1 is structure of reactor schematic diagram of the present invention；
Fig. 2 is inside reactor circle thermofin tubular construction schematic diagram of the present invention；
Fig. 3 is inside reactor side-fed structure of distributor schematic diagram of the present invention.
In accompanying drawing, the list of parts representated by each label is as follows：
1：Reactor shell
2：Circular thermofin pipe
2-1：Heat-transfer pipe medium entrance
2-2：Heat-transfer pipe media outlet
2-3：Horizontal thermofin pipe
3：Supporting screening plate
4：Side-fed distributor
4-1：Main feed pipe
4-2：Straight tube
5：Heat tracing coil pipe
5a：Heat tracing coil media charging aperture
5b：Heat tracing coil media discharging opening
6：Bracing ring
14~34：Distributor charging aperture
11a~33a：Import
11b~33b：Outlet
V1~v3：Total valve
V11~v33：Heat transfer medium charging aperture valve
V14~v34：Distributor charging aperture valve
A：Enterprising material mouth
B：Lower discharge port
C1~c3：Beds
Embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
As shown in Figure 1 to Figure 3, the new fixed bed reactors of a kind of catalytic oxidation of hydrogen chloride for preparing chlorine gas, including reactor cylinder
Body 1, upper cover 1-1, low head 1-2, multiple supporting screening plates 3, multiple side-fed distributors 4 and it is multigroup be used for supply or remove
The heat exchanger tube of inside reactor heat,
The reactor shell 1 is vertically arranged, and the top of reactor shell 1 is provided with the upper cover 1-1, its bottom
The low head 1-2 is installed；Enterprising material mouth A for being passed through unstrpped gas, the lower envelope are installed on the upper cover 1-1
The lower discharge port A that generation gas is reacted for discharging is installed on head 1-2,
The supporting screening plate 3 is horizontally fixed in the reactor shell 1, and multiple supporting screening plates 3 are along the reaction
The reactor shell 1 is axially divided into multilayer by device cylinder 1, is filled with catalyst on each supporting screening plate 3, every layer
The catalytic inner is provided with multigroup heat exchanger tube, and the heat exchanger tube is horizontally disposed in the catalyst, multigroup heat exchange
Pipe is axially evenly distributed in the catalyst along the reactor shell 1；The side-fed distributor 4 is horizontally fixed on institute
State in reactor shell 1 and positioned at close to the lower section of the supporting screening plate 3, the side-fed distributor 4 and the support screen
3 numbers of plate are identical and correspond, and the bottom of the side-fed distributor 4 is fixed with annular brace circle 6, the bracing ring 6
It is fixedly connected with the inwall of reactor shell 1.
The heat exchanger tube is provided with the import for being used to be passed through heat transfer medium for being oppositely arranged on both sides and discharge heat transfer medium
Outlet, the import and the outlet extend through the catalyst and stretch out the outside of the reactor shell 1；The import
Place is provided with heat transfer medium imported valve, and the imported valve in every layer of catalyst after pipeline parallel connection by main valve by being gated
System；The total valve of each layer is connected in parallel by pipeline.
The side-fed distributor 4 includes main feed pipe 4-1 and multiple straight tube 4- being parallel to each other at grade
2, described main feed pipe 4-1 one end is provided with distributor charging aperture, other end sealing；The distributor charging aperture runs through the reaction
Device cylinder 1 is simultaneously protruding, and distributor charging aperture valve is provided with the distributor charging aperture；Multiple straight tube 4-2 are certainly
One end of the main feed pipe 4-1 sealings, which is risen, to be uniformly fixed on towards the other end on the main feed pipe 4-1, the straight tube 4-2
It is closed at both ends, be fixed in the middle part of the straight tube 4-2 on the main feed pipe 4-1 and be connected with the main feed pipe 4-1；
Plane where the straight tube 4-2 is parallel with the cross section of reactor shell 1；The straight tube 4-2 bottoms are provided with multiple uniform points
The charging hole of cloth；Multiple straight tube 4-2 end is each attached to the top of the bracing ring, the bracing ring be fixed on recklessly
On the madial wall of reactor shell 1；The side-fed distributor 4 matches with the inner shape of reactor shell 1.
A diameter of 0.5~20mm of the charging hole；The internal diameter of the straight tube 4-2 is 20~100mm, two neighboring described
The distance between straight tube 4-2 is 50~500mm, and the length of the straight tube 4-2 is 200~1800mm, positioned at the described straight of centre
Pipe 4-2 length is most long, and the straight tube 4-2 gradually successively decreases from middle to both sides；The main feed pipe 4-1 internal diameters be 20~
100mm, its length are 800~2200mm；The internal diameter of the main feed pipe 4-1 is identical with the internal diameter of the straight tube 4-2.
The bottom margin of supporting screening plate 3 is fixed on the inner side of reactor shell 1 by multiple right angle pads, described straight
For angle pad while being fixed on the bottom margin of supporting screening plate 3, its another side is fixed on the inner side of reactor shell 1；It is described
Supporting screening plate 3 is circular hole punched holes type plate, and the aperture of the circular hole is 0.2~20mm.
The supporting screening plate 3 has 2~5, and the side-fed distributor 4 has 2~5, and the heat exchanger tube has 6~25
The reactor shell 1 is axially divided into 2~5 layers along the reactor shell 1, urged described in every layer by group, the supporting screening plate 3
2~5 groups of heat exchanger tubes are installed, the heat exchanger tube is horizontally disposed in the catalyst, heat exchanger tube described in 2~5 groups inside agent
Axially it is evenly distributed on along the reactor shell 1 in the catalyst；The internal diameter of the reactor shell 1 be 500mm~
2000mm, its axial height are 4500mm~18000mm；The height of the catalyst is 500mm~1500mm.
The axial distance of the side-fed distributor 4 and catalyst is 400~1000mm.
As shown in figure 1, reactor shell 1 is divided into 3 sections in the axial direction by supporting screening plate 3, for clearer this hair of explanation
It is bright, three catalyst layers are distinguished with label C1-C3 from top to bottom, the number of regions separated here is not limited to 3 sections, is preferably
2-5 sections.Each supporting screening plate 3 is used for separating beds, and supporting screening plate 3 is the disc for being provided with multiple 3-20mm apertures
Structure, one side-fed distributor 4 and bracing ring 5 are installed against the bottom of supporting screening plate 3.Side distributor is entered from top to bottom
Material mouth 4 is marked as 14~34.
The 1 available material of reactor shell is 304,316L or Hastelloy etc., the oval low head of its bottom
Spiraled heat tracing coil pipe for outer surface, and the heat tracing coil pipe 5, which spirals, to be welded on the outside of the low head 1-2, on the disk of heat tracing coil pipe 5
Provided with heat tracing feed pipe inlet 5a and heat tracing pipe outlet 5b, heat tracing medium is filled with the heat tracing coil pipe 5；The heat tracing
The internal diameter of coil pipe 5 is 10~60mm.In hydrogen chloride and the reacted device layer of oxygen during catalytic oxidation, due to Action of Gravity Field
The liquid depositions such as hydrochloric acid are had in bottom bulkhead, hydrops severe corrosion equipment；To prevent hydrops from producing, low head 1-2 outer surfaces
Heat tracing of spiraling coil pipe 5, the heat tracing coil pipe 5 may be set to hemispherical spiral and be welded on circular head, and its coil shape can
According to circumstances set, heat tracing medium can be fused salt, steam, conduction oil etc., and preferably steam, conduction oil is situated between as coil pipe heat tracing
Matter, more preferably conduction oil are as heat tracing medium, and the temperature stabilization of conduction oil is at 280~350 DEG C, preferably 300~320 DEG C.
Multiple be uniformly distributed and horizontally disposed circular heat transfer fin is installed in each beds (c1~c3)
Piece pipe 2, circular 2 numbers of thermofin pipe are three but are not limited to three in Fig. 1, and the circular thermofin pipe 2 includes relative
It is arranged on same plane and positioned at the first circular arc fin pipeline 2-1, the second circular arc fin pipeline 2-2 of both sides and multiple
Be parallel to each other straight fins pipeline, and the straight fins pipeline is fixed on the first circular arc fin pipeline 2-1 and the second circular arc
Between fin pipeline 2-2；The first circular arc fin pipeline 2-1 and the second circular arc fin pipeline 2-2 size, shape phase
Together, phase between the first circular arc fin pipeline 2-1, the second circular arc fin pipeline 2-2 and multiple straight fins pipelines
Intercommunicated, one end of the first circular arc fin pipeline 2-1 passes through the straight fins pipeline and the second circular arc fin
Pipeline 2-2 is connected, and the other end of the first circular arc fin pipeline 2-1 extends radially outward out composition and is passed through shifting heat Jie
The import of matter, the import is through the catalyst and stretches out outside the reactor shell 1；The second circular arc fin
Pipeline 2-2 one end is connected by the straight fins pipeline with the first circular arc fin pipeline 2-1, second circular arc
The shape fin pipeline 2-2 other end extends radially outward out the outlet of composition discharge heat transferring medium, and the outlet runs through
The catalyst simultaneously stretches out the reactor shell 1.
Circular thermofin pipe 2 is staggered along the axial direction of reactor shell 1 described in adjacent two groups, two adjacent groups institute
Angle is 30~120 between stating circular thermofin pipe 2°；The internal diameter of the circular thermofin pipe 2 is 25~100mm, adjacent
The distance between two described circular thermofin pipes 2 are 50~1000mm.
Outwards to heat when course of reaction reaction bed temperature is higher than heat-transfer medium temperature, reaction bed temperature is less than biography
During heat medium temperature, from heat transfer medium by circular thermofin pipe 2 to beds heat supply, in the process of running can be all the time
Temperature is in 250 DEG C of ＞ in holding reactor shell 1, thus can effectively prevent the generation of hot hydrochloric acid.
For the clearer explanation present invention, in Fig. 1 by the import of the circular thermofin pipe 2 of different layers catalyst,
Outlet, heat transfer medium charging aperture difference label, the from top to bottom heat transfer on the thermofin pipe 2 in different catalysts bed
Feed pipe inlet is to enter marked as 11a~33a, discharging opening marked as 11b~33b, total valve marked as v1~v3, heat transfer medium
Material mouth valve is marked as v11~v33, and distributor charging aperture valve is marked as v14~v34.Wherein each heat transfer medium charging aperture
11a~33a is controlled by heat transfer medium charging aperture valve v11~v33, when temperature anomaly occurs in some beds, is opened
The heat transfer medium charging aperture valve v11~v33 for opening corresponding bed carrys out the flow of Heat Transfer Control medium to reach control reactor temperature
Degree is stable and improves the purpose of reaction efficiency.
Preferably, supporting screening plate 3 is circular hole punching type plate, supporting catalyst that can be good, and ensure reaction fully after
It is continuous to carry out downward or upward.The bottom of supporting screening plate 3 immediately side-fed distributor 4, is distributed with a diameter of 40~60mm thereon
Circular port.The bottom of side-fed distributor 4 is provided with bracing ring 6 and is used for ensureing supporting screening plate 3 and side-fed distributor 4
Stability.Due to that long lasting for reaction the catalytic performance of catalyst can be caused constantly to reduce from top to bottom, multilayer is set to feed
Mouth carries out multiple feed, and its side-fed distributor 4 then passes through valve v14~v34 according to specific response situation and carries out selectivity
Open.
The catalyst of the preparing chlorine by oxidizing hydrogen chloride can be used with active Al2O3For carrier, Cu is active component, lead, manganese etc.
For the catalyst of coagent.
Particularly, due to the lasting use of catalyst, the continuous punching of its active component gas phase flow media in reactor
It can assemble under brush effect to reactor exit, catalyst is used and equipment operation brings adverse effect.Work as catalyst inactivation
Phenomenon goes out when to reactor middle and lower part, this invention takes the method for upper and lower charging order commutation, i.e., using lower discharge port B as
Material inlet, the enterprising material mouth A on reactor top as discharging opening, the charging of its side distributor charging aperture 14~34 according to
Catalyst inactivation situation is opened successively.
A kind of preparing chlorine by oxidizing hydrogen chloride novel reactor of the present invention is according to its use of embodiment and the course of work
For：
Hydrogen chloride and preheated to 300~350 DEG C of oxygen feed gas, catalysis is entered by the enterprising material mouth A in such as Fig. 1
Catalytic oxidation is carried out in agent bed C1, reaction temperature is 350~420 DEG C, is reacted for exothermic reaction, heat transferring medium is by passing through
The circular thermofin pipe 2 for being through at bed removes heat caused by reaction in time, ensure that reacting balance is efficiently carried out.Most
The mixed gas such as end-product chlorine, hydrogen chloride and vapor flow out through low head, the valve of heat tracing coil pipe 5 at the ellipsoidal head of bottom
In normally open, heat transfer medium enters from 5a, 5b outflows, ensure that reactor lower part hydrops will not produce.
With the passage in reaction time, inactivation occurs from top to bottom for catalyst causes reaction efficiency to reduce.It may be selected this moment
Property carry out side-fed, and can by reactor import and export exchange, carry out reversely charging, so doing can be with the efficient profit of high degree
With catalyst, extend the service life of catalyst.
A kind of embodiment of the present invention：
Below, the present invention is described in more details using embodiment, but the present invention is not limited by the embodiment
It is fixed.
As preparing chlorine by oxidizing hydrogen chloride novel reactor, using with identical reactor shown in Fig. 1, the reactor shell
Axial length is 8000mm, and internal diameter 1400mm, material used is 304 stainless steels.When different from Fig. 1, each layer dress of reactor
There is temperature sensor to show bed temperature in time, ensure the efficient progress of reaction.In addition, beds are provided with hand up and down
Hole, for facilitating the handling of catalyst.
Whole reactor is divided into 3 layers by the sieve plate of centre installation, and every layer of catalyst filling is highly 1000mm, supporting screening plate
The circular port that 2mm is disposed with 3 is used for ensureing while catalyst is not fallen out and does not influence passing through for reaction product.Against sieve
Plate bottom is provided with side-fed distributor, feeds bore 50mm, and 2mm circular port is uniformly provided with distributor.Each urge
Average mark is furnished with 3 groups of transverse direction heat-exchange finned tubes in agent bed, bore 32mm, two adjacent groups thermofin pipe axially away from
From for 200mm, 3 groups of finned tubes are 90 ° in reactor axial angle.In addition, it is designed with every group of finned tube and feed distributor
Valve controls rate-of flow, and multiple temperature sensors instruction bed temperatures are provided with bed.Installed at the ellipse head of bottom
There is heat tracing pipe, prevent thering is hydrops to accelerate reactor corrosion in course of reaction.
The valve of the heat transfer coils of each layer beds is opened, the conduction oil that temperature is about 350 DEG C is imported, catalyst
Bed slowly heats up therewith, when temperature sensor displays temperature is about 320 DEG C, closes heat conduction oil-in, is about by flow
(mass ratio of hydrogen chloride and oxygen is 2 for 2697kg/h hydrogen chloride and the mixture of oxygen：1) 300 DEG C are preheating to, from reactor
Upper inlet A enters first layer beds and carries out preparing chlorine by oxidizing hydrogen chloride reaction, and side feed opening is closed, and reaction turns
Rate is 80~90%, and oxygen, the 1641kg/h chlorine of hydrogen chloride, 452kg/h that flow is about 187kg/h are obtained after reaction
Flowed out with 417kg/h vapor from the lower part outlet B of reactor, reaction keeps pressure to be carried out under 0.3MPa, is now catalyzed
Agent bed temperature starts slowly to rise, and is again turned on conduction oil valve, and the conduction oil for being about 230~280 DEG C by temperature is imported into
In heat exchange, controlling opening of valve, reaction temperature is kept between 400~420 DEG C, meanwhile, open lower ellipse head heat tracing pipe
The conduction oil that temperature is 250 DEG C is passed through by valve, ensures that end socket exit will not produce hydrops and accelerate corrosion.
With the progress of reaction, top-down slowly inactivation occurs for catalyst, and reactor outlet raw material composition is changed into
281kg/h hydrogen chloride, 472kg/h oxygen, 1550kg/h chlorine and 394kg/h vapor, reaction target product have
Reduced, show that the bed of catalyst first inactivates.Now, reactor upper feed inlet A is closed, opens the second catalyst bed
The side-fed distributor that layer is provided with, mass flow and concentration keep constant and enter the second beds from there, instead
Product composition is answered to be changed into 235kg/h hydrogen chloride, 462kg/h oxygen, 1595kg/h chlorine and 405kg/h vapor,
Show that catalyst activity has rising by a small margin, the increase of target product chlorine gas concentration.Likewise, as reaction is carried out, second
Bed catalyst also occurs slowly to inactivate, and now opens the valve of third layer side-fed distributor, closes second layer side and enters
Expect distributor valve, close material outlet B, open material inlet A, realize the exchange of inlet and outlet position.Under the conditions of such a, observation
The concentration of chlorine starts rising by a small margin occur again in material outlet.
With the progress of reaction, each layer catalyst inactivation is deepened, when reacting material outlet concentration is reduced to 375kg/h chlorination
Hydrogen, 493kg/h oxygen, 1458kg/h chlorine and 371kg/h vapor when, stop reaction and carry out catalyst activity component
Load again to recover its reactivity.Nitrogen is blown into from reactor upper feed inlet A, remains lower ellipse head companion
The valve opening of heat pipe, question response device temperature slowly drop to less than 60 DEG C, and hydrogen chloride and chlorine gas concentration in outlet material
During not higher than 0.1%, the hand hole being equipped with each layer beds is opened, each layer catalyst is taken out and loaded again.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, it is characterised in that including reactor shell, upper envelope
Head, low head, multiple supporting screening plates, multiple side-fed distributors and it is multigroup be used for supply or remove inside reactor heat
Heat exchanger tube,
The reactor shell is vertically arranged, and the upper cover is provided with the top of the reactor shell, and its bottom is installed
State low head；Enterprising material mouth for being passed through unstrpped gas is installed on the upper cover, is provided with and is used on the low head
The lower discharge port of discharge reaction generation gas,
The supporting screening plate is horizontally fixed in the reactor cylinder body, and multiple supporting screening plates are along the reactor shell axle
Multilayer is divided into by the reactor shell, catalyst, every layer of catalytic inner are filled with each sieve plate
Multigroup heat exchanger tube is installed, the heat exchanger tube is horizontally disposed in the catalyst, and multigroup heat exchanger tube is along the reactor
Cylinder is axially evenly distributed in the catalyst；The side-fed distributor be horizontally fixed in the reactor cylinder body and
Positioned at close to the lower section of the supporting screening plate, the side-fed distributor is identical with the supporting screening plate number and one a pair
Should, the bottom of the side-fed distributor is fixed with annular brace circle, and the bracing ring is consolidated with the reactor shell inwall
Fixed connection.
A kind of 2. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterised in that institute
State heat exchanger tube and be provided with the import for being used to be passed through heat transfer medium for being oppositely arranged on both sides and the outlet of discharge heat transfer medium, it is described
Import and the outlet extend through the catalyst and stretched out on the outside of the reactor shell；The entrance is provided with heat transfer and is situated between
Matter imported valve, the imported valve in every layer of catalyst by after pipeline parallel connection by main valve gate control；The institute of each layer
Total valve is stated to be connected in parallel by pipeline.
A kind of 3. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 2, it is characterised in that institute
It is circular thermofin pipe to state heat exchanger tube, and the circular thermofin pipe includes being oppositely arranged on same plane and positioned at both sides
First circular arc fin pipeline, the second circular arc fin pipeline and multiple straight fins pipelines that are parallel to each other, the straight fins pipe
Road is fixed between the first circular arc fin pipeline and the second circular arc fin pipeline；The first circular arc fin pipeline
It is identical with size, the shape of the second circular arc fin pipeline, the first circular arc fin pipeline, the second circular arc fin pipeline
It is interconnected between multiple straight fins pipelines, one end of the first circular arc fin pipeline passes through the straight fins pipe
Road is connected with the second circular arc fin pipeline, and the other end of the first circular arc fin pipeline extends radially outward
Go out and form the import for being passed through and moving thermal medium, the import is through the catalyst and stretches out the reactor shell；It is described
One end of second circular arc fin pipeline is connected by the straight fins pipeline with the first circular arc fin pipeline, described
The other end of second circular arc fin pipeline extends radially outward out the outlet of composition discharge heat transferring medium, the outlet
Through the catalyst and stretch out the reactor shell.
A kind of 4. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 3, it is characterised in that phase
Circular thermofin pipe described in adjacent two groups is staggered along reactor shell axial direction, circular heat transfer fin described in two adjacent groups
Angle is 30~120 ° between piece pipe；The internal diameter of the circular thermofin pipe is 25~100mm, the two neighboring circular biography
The distance between hot finned tube is 50~1000mm.
A kind of 5. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterised in that institute
Stating side-fed distributor includes main feed pipe and multiple straight tubes being parallel to each other at grade, described main feed pipe one end
Provided with distributor charging aperture, other end sealing；The distributor charging aperture is described through the reactor shell and protruding
Distributor charging aperture valve is installed in distributor charging aperture；Multiple straight tubes from one end of the main feed seal of tube to
The other end uniformly to be fixed on the main feed pipe, the straight tube it is closed at both ends, be fixed in the middle part of the straight tube described
It is connected on main feed pipe and with the main feed pipe；Plane where the straight tube is parallel with the reactor shell cross section；
The straight tube bottom is provided with multiple equally distributed charging holes；The end of multiple straight tubes is each attached to the top of the bracing ring
Portion, the bracing ring are fixed on the madial wall of the reactor shell；The side-fed distributor and the reactor cylinder
Body inner shape matches.
A kind of 6. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 5, it is characterised in that institute
State a diameter of 0.5~20mm of charging hole；The internal diameter of the straight tube is 20~100mm, between the two neighboring straight tube away from
It is 200~1800mm from the length for 50~500mm, the straight tube, the length positioned at the straight tube of centre is most long, described straight
Pipe gradually successively decreases from middle to both sides；The main feed bore is 20~100mm, and its length is 800~2200mm.
A kind of 7. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterised in that institute
State and heat tracing coil pipe is installed on the outside of low head, the heat tracing coil pipe, which spirals, to be welded on the outside of the low head, the heat tracing coil pipe
Disk is provided with heat tracing feed pipe inlet and heat tracing pipe outlet, and heat tracing medium is filled with the heat tracing coil pipe；The heat tracing
The internal diameter of coil pipe is 10~60mm.
A kind of 8. new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterised in that institute
State supporting screening plate bottom margin to be fixed on the inside of the reactor shell by multiple right angle pads, the right angle pad is while solid
The supporting screening plate bottom margin is scheduled on, its another side is fixed on the inside of the reactor shell；The supporting screening plate is circular hole
Punched holes type plate, the aperture of the circular hole is 0.2~20mm.
9. according to a kind of any one of claim 1 to 8 new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, it is special
Sign is that the supporting screening plate has 2~5, and the side-fed distributor has 2~5, and the heat exchanger tube has 6~25 groups, institute
State supporting screening plate and the reactor shell is axially divided into 2~5 layers along the reactor shell, every layer of catalytic inner
2~5 groups of heat exchanger tubes are installed, the heat exchanger tube is horizontally disposed in the catalyst, and heat exchanger tube described in 2~5 groups is along described anti-
Device cylinder is answered axially to be evenly distributed in the catalyst；The internal diameter of the reactor shell is 500mm~2000mm, its axial direction
Highly it is 4500mm~18000mm；The height of the catalyst is 500mm~1500mm.
10. according to a kind of any one of claim 1 to 8 new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, its
It is characterised by, the axial distance of the side-fed distributor and catalyst is 400~1000mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610058441.6A CN105776141B (en) | 2016-01-27 | 2016-01-27 | A kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610058441.6A CN105776141B (en) | 2016-01-27 | 2016-01-27 | A kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105776141A CN105776141A (en) | 2016-07-20 |
| CN105776141B true CN105776141B (en) | 2018-03-09 |
Family
ID=56402557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610058441.6A Expired - Fee Related CN105776141B (en) | 2016-01-27 | 2016-01-27 | A kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776141B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117580B (en) * | 2017-03-31 | 2019-04-19 | 万华化学集团股份有限公司 | A method of chloration hydro-oxidation is carried out using trickle bed reactor and prepares chlorine |
| CN107930540A (en) * | 2017-11-07 | 2018-04-20 | 四川金象赛瑞化工股份有限公司 | A kind of controlling temp type multilayer FCC reactor |
| CN109289713B (en) * | 2018-10-18 | 2021-04-20 | 辽宁石油化工大学 | Mosquito-repellent incense coil isothermal reactor and using method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10361519A1 (en) * | 2003-12-23 | 2005-07-28 | Basf Ag | Process for the production of chlorine by gas phase oxidation of hydrogen chloride |
| WO2009010168A1 (en) * | 2007-07-13 | 2009-01-22 | Bayer Technology Services Gmbh | Method for producing chlorine by multi step adiabatic gas phase oxidation |
-
2016
- 2016-01-27 CN CN201610058441.6A patent/CN105776141B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105776141A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4651889B2 (en) | Isothermal reactor for exothermic or endothermic heterogeneous reactions | |
| CN106622044B (en) | Ammoxidation reactor and nitrile compound preparation method | |
| US8071059B2 (en) | Chemical reactor | |
| CN105776141B (en) | A kind of new fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas | |
| CN101254442B (en) | Use of gas-solid catalytic reactor in preparing methanol | |
| CN103990420A (en) | Multitubular fixed bed reactor and application thereof | |
| CN105032305A (en) | Novel radial plate type reactor | |
| CN203990548U (en) | radial parallel catalytic reactor | |
| CN105536654B (en) | A kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor | |
| CN101769694B (en) | Forced internal recirculation type external cooler for catalytic cracking catalyst | |
| CN113426384A (en) | Multi-section fixed bed reactor and Fischer-Tropsch synthesis reaction system | |
| CN107930540A (en) | A kind of controlling temp type multilayer FCC reactor | |
| CN103240036A (en) | Temperature stress resistant heat transfer reactor and composite device and application thereof | |
| CN1736574A (en) | Non-hot spot calandria type fixed bed reactors | |
| CN1363416A (en) | Heterogeneous reactor for heat absorption or release | |
| CN103341341A (en) | Fluidized bed reactor for preparing butadiene | |
| CN207941495U (en) | A kind of shell and tube reactor with double helix baffle plate | |
| CN101371094B (en) | Reactor or heat exchanger with improved local heat transfer performance | |
| CN105413592B (en) | A kind of combined type fixed bed reactors and the device formed by it | |
| CN209205255U (en) | A kind of multistage temperature control converter of mercury-free catalytic production vinyl chloride | |
| CN209197538U (en) | A kind of fluidized bed external warmer that baffle plate is strengthened | |
| CN207169658U (en) | Efficient HPPO device reaction devices | |
| CN103172072B (en) | Realize reactor and the method for chlorosilane synthesis | |
| CN107376792A (en) | Efficient HPPO device reaction device equipment | |
| CN206810238U (en) | A kind of fixed bed hydrogenation prepares cyclohexanone system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180309 Termination date: 20190127 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |