CN105776141A - Novel fixed bed reactor for preparing chlorine gas through catalytic oxidation of hydrogen chloride - Google Patents
Novel fixed bed reactor for preparing chlorine gas through catalytic oxidation of hydrogen chloride Download PDFInfo
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- CN105776141A CN105776141A CN201610058441.6A CN201610058441A CN105776141A CN 105776141 A CN105776141 A CN 105776141A CN 201610058441 A CN201610058441 A CN 201610058441A CN 105776141 A CN105776141 A CN 105776141A
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- 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
Abstract
The invention relates to a novel fixed bed reactor for preparing chlorine gas through catalytic oxidation of hydrogen chloride; a reactor cylinder body is divided into multiple layers by supporting sieve plates in the axial direction; each layer of the sieve plate is filled with a catalyst, and each layer of catalyst is internally provided with a plurality of groups of heat exchange tubes for supplying or removing reactor internal heat to ensure that the reaction temperature is in a required range; a side face feed distributor is mounted in a manner of clinging to the lower part of each sieve plate. By adjusting the side face feeding quantity, the catalytic activity of each layer of catalyst is guaranteed; the lower parts of the sieve plates and the side face feed distributors are fixed by round support rings to ensure that side face feeding has enough space for evenly mixing. The reactor can effectively uniformly remove heat generated by a catalytic reaction, enhances the heat and mass transfer efficiency, reduces the flow resistance, achieves a good temperature control effect, and makes full use of the reactor space to disperse reaction materials to the largest extent; and with multi-bed-layer feeding, the service life of the catalyst is extended, besides, the equipment investment is reduced, and the production cost is saved.
Description
Technical field
The invention belongs to technical field of chemical, be specifically related to a kind of novel fixed bed reactors for preparing chlorine by catalytic oxidation of hydrogen chloride.
Background technology
Since Deacon (1886) catalytic oxidation of hydrogen chloride for preparing chlorine gas art inventions, around two large-engineering problems of this technique: durability catalyst preparation and the design of high-performance reactor, always among constantly exploration and improvement.Wherein reactor aspect, owing to hydrogen chloride Catalytic Oxygen process is strong exothermal reaction, in device, reactor is had very severe corrosive by reaction medium under the high temperature conditions, thus the material and operating condition to reactor requires harsher.It addition, effectively removing and control to temperature of reactor of reaction heat, also the structural design of reactor is proposed significantly high requirement.Therefore temperature of reactor controls and the application of equipment material is the key technology of catalytic oxidation of hydrogen chloride for preparing chlorine gas, but research and development in this regard up to now also lag far behind industry actual demand.
For reactor fluidized-bed reactor and the fixed bed reactors two types of preparing chlorine by oxidizing hydrogen chloride, fixing bed is big owing to processing, and cost is low and operates relatively easy and attention.
The ruthenium-oxide that uses of patent EP1894885A system SUMITOMO CHEMICAL chemistry exploitation makes the shell and tube reactor of catalyst.This reactor is the design of vertical row tubular type multistage heat transfer chamber, the not intercommunication of each heat transfer chamber, within it pass into fused salt heat-conducting medium and remove the produced heat of reaction, the melted flow regulated in each heat transfer chamber is relied on to realize the control of each section of temperature of reactor, thus realizing the adjustment to whole temperature of reactor curve.Owing to the inducer reactant concentration of reactor is higher, react comparatively violent, temperature rise is very fast, in tubulation, the activity of the ruthenium catalyst that the heat conductivity of filling is higher wants segmentation adjustment, the ruthenium content ratio of catalyst is adjusted to the bottom 100% of reactor from the 40% of reactor head, the pressure of whole reactor is 0.1～1.0MPa, and temperature is 200～500 DEG C.Although reaction bed temperature can be controlled in satisfied degree by the method, but structure is complicated, involves great expense, and operation controls loaded down with trivial details.More be limited to ruthenium catalyst activity regulate difficulty in catalyst preparing.
Patent WO2013004651A1 describes the catalyst of cerium-carrying and ruthenium and applies at the middle the catalytic oxidation of hydrogen chloride of the miniature isothermal reactor of bundled tube, it is proposed to patent EP1894885A very similar approach, bundled tube reactor is divided into 2～10 conversion zones.With the catalyst of cerium-carrying in internal diameter 8mm, in the reactor of height 1000mm, it is 0.75 at feed rate ratio O2/HCl, reaction temperature≤420 DEG C, when reaction pressure 2～10bar, the conversion ratio of hydrogen chloride is carried out the experiment test of a series of different reactor temperature section, it is believed that keep higher reaction temperature to be conducive to improving the conversion ratio of hydrogen chloride for cerium catalyst.But this patent fails to provide concrete structure and the operational approach of the isothermal reactor used.
Patent CN102134057A proposes a kind of high temperature resistant, erosion resistant and corrosion resistant reactor, adds external thermal insulation to reduce heat radiation on wall, and inwall then adds, anti-wear.But the heat that this reactor fails that reaction is generated is done heat transfer timely and effectively and is processed, and is easily caused catalyst local temperature too high and inactivate.It addition, the secondary corrosion that reaction medium is not penetrated into metallic reactors wall from inner liner by this patent is likely to do further consideration.
Based on case above, it is known that needing the more efficient preparing chlorine by oxidizing hydrogen chloride reactor of one, it has can remove heat of reaction in time, control to adjust reaction temperature well, and the advantage such as cheap, easy to use.
Summary of the invention
The technical problem to be solved is to provide one can effectively remove exothermic heat of reaction, effectively controls reaction bed temperature, reduces catalyst bed layer resistance and can make full use of space reactor and make the uniform the catalytic oxidation of hydrogen chloride novel reactor of mixing of materials.
The technical scheme is that a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, including reactor shell, upper cover, low head, multiple supporting screening plate, multiple side-fed distributor and many groups for supplying or remove the heat exchanger tube of inside reactor heat
Described reactor shell is vertically arranged, and described reactor shell top is provided with described upper cover, is provided with described low head bottom it；Described upper cover is provided with the upper feeding mouth for passing into unstrpped gas, described low head is provided with the lower discharge port generating gas for discharging reaction,
Described supporting screening plate is horizontally fixed in described reactor cylinder body, described reactor shell is axially divided into multilamellar along described reactor shell by multiple described supporting screening plates, each described sieve plate is all filled with catalyst, every layer of described catalytic inner is provided with and organizes heat exchanger tube more, described heat exchanger tube is horizontally disposed with in the catalyst, and the described heat exchanger tube of many groups is axially evenly distributed in described catalyst along described reactor shell；Described side-fed distributor is horizontally fixed in described reactor cylinder body and is located close to the lower section of described supporting screening plate, described side-fed distributor is identical with described supporting screening plate number and one_to_one corresponding, the bottom of described side-fed distributor is fixed with annular brace circle, and described bracing ring is fixing with described reactor shell inwall to be connected.
On the basis of technique scheme, the present invention can also do following improvement:
Further, described heat exchanger tube is provided with the outlet of the import and discharge heat transfer medium for the passing into heat transfer medium that are oppositely arranged on both sides, and described import and described outlet extend through described catalyst and stretch out outside described reactor shell；Described import department is provided with heat transfer medium imported valve, the described imported valve in every layer of described catalyst by after pipeline parallel connection by total valve control；The described total valve of each layer is connected in parallel by pipeline.
Further, described heat exchanger tube is circular thermofin pipe, described circular thermofin pipe includes being oppositely arranged in the same plane and be positioned at the first circular arc fin pipeline of both sides, the second circular arc fin pipeline and multiple straight fins pipeline that is parallel to each other, and described straight fins pipeline is fixed between described first circular arc fin pipeline and the second circular arc fin pipeline；Described first circular arc fin pipeline and the size of the second circular arc fin pipeline, shape are identical, it is interconnected between described first circular arc fin pipeline, the second circular arc fin pipeline and multiple described straight fins pipeline, one end of described first circular arc fin pipeline is connected with described second circular arc fin pipeline by described straight fins pipeline, the other end of described first circular arc fin pipeline extends radially outward out composition and passes into the described import moving thermal medium, and described import runs through described catalyst and stretches out described reactor shell；One end of described second circular arc fin pipeline is connected with described first circular arc fin pipeline by described straight fins pipeline, the other end of described second circular arc fin pipeline extends radially outward out composition and discharges the described outlet of heat transferring medium, and described outlet runs through described catalyst and stretches out described reactor shell.
Further, described in adjacent two groups, circular thermofin pipe is crisscross arranged along reactor shell axial direction, and described in two adjacent groups, between circular thermofin pipe, angle is 30～120 °；The internal diameter of described circular thermofin pipe is 25～100mm, and the distance between adjacent two described circular thermofin pipes is 50～1000mm.
Further, described side-fed distributor includes main feed pipe and multiple straight tube being parallel to each other at grade, and described main feed pipe one end is provided with distributor charging aperture, and the other end seals；Described distributor charging aperture runs through described reactor shell and protruding, and described distributor charging aperture is provided with distributor charging aperture valve；Multiple described straight tubes are uniformly fixed on described main feed pipe towards the other end from one end of the described main feed seal of tube, the closed at both ends of described straight tube, and the middle part of described straight tube is fixed on described main feed pipe and is connected with described main feed pipe；Described straight tube place plane is parallel with described reactor shell cross section；Multiple equally distributed charging hole it is provided with bottom described straight tube；The end of multiple described straight tubes is each attached to the top of described bracing ring, described bracing ring be fixed on recklessly reactor shell medial wall on；Described side-fed distributor and described reactor shell inner shape match.
Further, the diameter of described charging hole is 0.5～20mm；The internal diameter of described straight tube is 20～100mm, and the distance between adjacent two described straight tubes is 50～500mm, and the length of described straight tube is 200～1800mm, and the length of centrally located described straight tube is the longest, and described straight tube gradually successively decreases to both sides from middle；Described main feed bore is 20～100mm, and its length is 800～2200mm.
Further, being provided with heat tracing coil pipe outside described low head, described heat tracing coil pipe spirals and is welded on outside described low head, and described heat tracing coil pipe dish is provided with heat tracing feed pipe inlet and heat tracing pipe outlet, is filled with heat tracing medium in described heat tracing coil pipe；The internal diameter of described heat tracing coil pipe is 10～60mm.
Further, described supporting screening plate bottom margin is fixed on inside described reactor shell by multiple right angles pad, and described right angle pad is fixed on described supporting screening plate bottom margin, and its another side is fixed on inside described reactor shell；Described supporting screening plate is circular hole punched holes type plate, and the aperture of described circular hole is 0.2～20mm.
Further, described supporting screening plate has 2～5, described side-fed distributor has 2～5, described heat exchanger tube has 6～25 groups, described reactor shell is axially divided into 2～5 layers along described reactor shell by described supporting screening plate, every layer of described catalytic inner is provided with 2～5 groups of heat exchanger tubes, and described heat exchanger tube is horizontally disposed with in the catalyst, and described in 2～5 groups, heat exchanger tube is axially evenly distributed in described catalyst along described reactor shell；The internal diameter of described reactor shell be 500mm～2000mm, its axial height is 4500mm～18000mm；The height of described catalyst is 500mm～1500mm.
Further, described side-fed distributor is 400～1000mm with the axial distance of catalyst.
Above-mentioned further scheme is adopted to provide the benefit that:
1. the heat-transfer pipe in beds is welded to form by many parallel fins pipes and ring main, heat transfer medium enters from ring main side, flowing out from opposite side ring main after flowing through each finned tube, the parallel-connection structure feature of many finned tubes increases the heat transfer area of heat transfer medium；Same, heat-transfer pipe adopts radially (being not limited to radially) finned tube, can effectively uniform conductive catalyst particle surface heat of reaction, raising heat transfer efficiency.
2. the circular interlaced setting of thermofin pipe described in adjacent two-layer, the angle that the described import of two described circular thermofin pipes is formed is 30 °～120 DEG C, it is preferred to 60～90 °, it is possible to makes beds heat radiation more uniform, eliminates hot Biased flow phenomenon.
3. the input concentration that can control catalyst bed interlayer of feed distributor between catalyst layer, makes material reaction more abundant, improves the conversion per pass of reactor, it is possible to coordinates thermofin pipe that the reaction temperature of reactor carries out auxiliary and adjusts.
4. between catalyst layer the another effect that of feed distributor can rise sharply in catalyst bed reaction temperature (industrial be referred to as " temperature runaway "), inert media (such as water vapour, nitrogen etc.) is introduced beds, effectively to suppress temperature of reactor, it is prevented that the excessive temperature infringement to catalyst.
5. along with catalyst uses the lengthening of time, its active component can be assembled to reactor exit under the continuous souring of gas phase flow media in reactor, catalyst is used and equipment runs and brings adverse effect.When catalysqt deactivation phenomenon goes out when to reactor middle and lower part, this invention takes the way of upper and lower charging order commutation, by the lower discharge port of bottom of reactor as charging aperture, the upper feeding mouth on reactor top is as discharging opening, and its side feed opening is sequentially carried out unlatching according to catalysqt deactivation situation.
The present invention also has the advantages that
(1) with the heat-transfer pipe parallel connection welding of fin and ring main, spiral compared with heat-transfer pipe with conventional one-channel, this heat-transfer pipe can effectively evenly remove the heat that catalytic reaction produces, enhance heat, matter transmission efficiency, reduce flow resistance, heat radiation uniformly, reaches good temperature control effect, it is prevented that hot-spot causes catalysqt deactivation or loss of active component in time.
(2) reactor of the present invention is due to fin heat transfer pipe group, heat is outwards given when reaction bed temperature is higher than heat-transfer medium temperature, when reaction bed temperature is lower than heat-transfer medium temperature, by heat transfer medium by finned tube to beds heat supply, running can remain reactor temperature > 250 DEG C, thus effectively prevent the generation of hot hydrochloric acid.Thus 304 or 316L rustless steel can be adopted, special nickelic with existing or compared with the reactor of tantalum metal material, simple in equipment, cost declines.Can be recycled as other thermal source from the heat of coil pipe removal, be effectively saved investment, reduce production cost.
(3) owing to the catalytic performance of catalyst can be caused constantly to reduce from top to bottom long lasting for reaction, multilamellar charging aperture is set and carries out multiple feed, and reactor import and export commutation charging, catalyst can be made full use of, to greatest extent prolongation catalyst service life.
(4) bracing ring is installed in direct mounted sieve bottom, side-fed distributor top, utilizes distributor supporting screening plate, significantly increases the distribution space of reaction mass, makes material have the time mixing of abundance, improves reaction efficiency.Meanwhile, distributor and the structure that sieve plate is two-in-one decrease one layer of bracing ring, have saved equipment investment compared with separating with traditional the two.
(5) reactor adopts and adds heat tracing coil pipe outside low head, can be effectively prevented the generation of hydrochloric acid when start-stop car or unusual service condition or gather, it is to avoid the local corrosion of reactor, being greatly prolonged the service life of reactor.
In sum, the invention has the beneficial effects as follows: this reactor effectively evenly removes the heat that catalytic reaction produces, enhance heat, matter transmission efficiency, reduce flow resistance, reaching good temperature control effect, and make full use of space reactor and make reaction mass farthest disperse, the charging of many beds can extend the service life of catalyst, reduce equipment investment simultaneously, save production cost.
Accompanying drawing explanation
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: upper feeding mouth
B: lower discharge port
C1～c3: beds
Detailed description of the invention
Below in conjunction with accompanying drawing, principles of the invention and feature being described, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
As shown in Figure 1 to Figure 3, a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, including reactor shell 1, upper cover 1-1, low head 1-2, multiple supporting screening plate 3, multiple side-fed distributor 4 and many groups for supplying or remove the heat exchanger tube of inside reactor heat
Described reactor shell 1 is vertically arranged, and described reactor shell 1 top is provided with described upper cover 1-1, is provided with described low head 1-2 bottom it；Described upper cover 1-1 is provided with the upper feeding mouth A for passing into unstrpped gas, described low head 1-2 is provided with the lower discharge port A generating gas for discharging reaction,
Described supporting screening plate 3 is horizontally fixed in described reactor shell 1, described reactor shell 1 is axially divided into multilamellar along described reactor shell 1 by multiple described supporting screening plates 3, each described supporting screening plate 3 is all filled with catalyst, every layer of described catalytic inner is provided with and organizes heat exchanger tube more, described heat exchanger tube is horizontally disposed with in the catalyst, and the described heat exchanger tube of many groups is axially evenly distributed in described catalyst along described reactor shell 1；Described side-fed distributor 4 is horizontally fixed in described reactor shell 1 and is located close to the lower section of described supporting screening plate 3, described side-fed distributor 4 is identical with described supporting screening plate 3 number and one_to_one corresponding, the bottom of described side-fed distributor 4 is fixed with annular brace circle 6, and described bracing ring 6 is fixing with described reactor shell 1 inwall to be connected.
Described heat exchanger tube is provided with the outlet of the import and discharge heat transfer medium for the passing into heat transfer medium that are oppositely arranged on both sides, and described import and described outlet extend through described catalyst and stretch out outside described reactor shell 1；Described import department is provided with heat transfer medium imported valve, the described imported valve in every layer of described catalyst by after pipeline parallel connection by total valve control；The described total valve of each layer is connected in parallel by pipeline.
Described side-fed distributor 4 includes main feed pipe 4-1 and multiple straight tube 4-2 being parallel to each other at grade, and described main feed pipe 4-1 one end is provided with distributor charging aperture, and the other end seals；Described distributor charging aperture runs through described reactor shell 1 and protruding, and described distributor charging aperture is provided with distributor charging aperture valve；Multiple described straight tube 4-2 are uniformly fixed on towards the other end on described main feed pipe 4-1 from described main feed pipe 4-1 one end sealed, the closed at both ends of described straight tube 4-2, the middle part of described straight tube 4-2 is fixed on described main feed pipe 4-1 and is connected with described main feed pipe 4-1；Described straight tube 4-2 place plane is parallel with described reactor shell 1 cross section；Multiple equally distributed charging hole it is provided with bottom described straight tube 4-2；The end of multiple described straight tube 4-2 is each attached to the top of described bracing ring, described bracing ring be fixed on recklessly reactor shell 1 medial wall on；Described side-fed distributor 4 matches with described reactor shell 1 inner shape.
The diameter of described charging hole is 0.5～20mm；The internal diameter of described straight tube 4-2 is 20～100mm, distance between adjacent two described straight tube 4-2 is 50～500mm, the length of described straight tube 4-2 is 200～1800mm, and the length of centrally located described straight tube 4-2 is the longest, and described straight tube 4-2 gradually successively decreases to both sides from middle；Described main feed pipe 4-1 internal diameter is 20～100mm, and its length is 800～2200mm；The internal diameter of described main feed pipe 4-1 is identical with the internal diameter of described straight tube 4-2.
Described supporting screening plate 3 bottom margin is fixed on inside described reactor shell 1 by multiple right angles pad, and described right angle pad is fixed on described supporting screening plate 3 bottom margin, and its another side is fixed on inside described reactor shell 1；Described supporting screening plate 3 is circular hole punched holes type plate, and the aperture of described circular hole is 0.2～20mm.
Described supporting screening plate 3 has 2～5, described side-fed distributor 4 has 2～5, described heat exchanger tube has 6～25 groups, described reactor shell 1 is axially divided into 2～5 layers along described reactor shell 1 by described supporting screening plate 3, every layer of described catalytic inner is provided with 2～5 groups of heat exchanger tubes, described heat exchanger tube is horizontally disposed with in the catalyst, and heat exchanger tube described in 2～5 groups is axially evenly distributed in described catalyst along described reactor shell 1；The internal diameter of described reactor shell 1 is 500mm～2000mm, and its axial height is 4500mm～18000mm；The height of described catalyst is 500mm～1500mm.
The axial distance of described side-fed distributor 4 and catalyst is 400～1000mm.
As it is shown in figure 1, reactor shell 1 is divided into 3 sections in the axial direction by supporting screening plate 3, for the clearer explanation present invention, by the use label C1-C3 differentiation from top to bottom of three catalyst layers, the number of regions all separated here is not limited to 3 sections, it is preferred to 2-5 section.Each supporting screening plate 3 is used for separating beds, and supporting screening plate 3 is the disc-shaped structure having multiple 3-20mm aperture, installs a side-fed distributor 4 and bracing ring 5 bottom supporting screening plate 3.From top to bottom side distributor charging aperture 4 is numbered 14～34.
The described available material of reactor shell 1 is 304,316L or Hastelloy etc., oval low head outer surface bottom it spirals heat tracing coil pipe, described heat tracing coil pipe 5 spirals and is welded on outside described low head 1-2, described heat tracing coil pipe 5 dish is provided with heat tracing feed pipe inlet 5a and heat tracing pipe outlet 5b, is filled with heat tracing medium in described heat tracing coil pipe 5；The internal diameter of described heat tracing coil pipe 5 is 10～60mm.In hydrogen chloride and the reacted device layer of oxygen in catalytic oxidation process, have the liquid depositions such as hydrochloric acid due to action of gravity in bottom bulkhead, hydrops severe corrosion equipment；For preventing hydrops from producing, low head 1-2 outer surface spirals heat tracing coil pipe 5, described heat tracing coil pipe 5 may be set to hemispherical spiraling and is welded on circular head, its coil shape can according to circumstances be arranged, heat tracing medium can be fused salt, steam, heat conduction wet goods, it is preferable that steam, conduction oil are as coil pipe heat tracing medium, and more preferably conduction oil is as heat tracing medium, the temperature stabilization of conduction oil is at 280～350 DEG C, it is preferable that 300～320 DEG C.
Multiple being uniformly distributed and horizontally disposed circular thermofin pipe 2 is installed in each described beds (c1～c3), in Fig. 1, circular thermofin pipe 2 number is three but is not limited to three, described circular thermofin pipe 2 includes being oppositely arranged in the same plane and be positioned at the first circular arc fin pipeline 2-1 of both sides, the second circular arc fin pipeline 2-2 and multiple straight fins pipeline that is parallel to each other, and described straight fins pipeline is fixed between described first circular arc fin pipeline 2-1 and the second circular arc fin pipeline 2-2；The size of described first circular arc fin pipeline 2-1 and the second circular arc fin pipeline 2-2, shape is identical, described first circular arc fin pipeline 2-1, it is interconnected between second circular arc fin pipeline 2-2 and multiple described straight fins pipeline, one end of described first circular arc fin pipeline 2-1 is connected with described second circular arc fin pipeline 2-2 by described straight fins pipeline, the other end of described first circular arc fin pipeline 2-1 extends radially outward out composition and passes into the described import moving thermal medium, described import runs through described catalyst and stretches out outside described reactor shell 1；One end of described second circular arc fin pipeline 2-2 is connected with described first circular arc fin pipeline 2-1 by described straight fins pipeline, the other end of described second circular arc fin pipeline 2-2 extends radially outward out composition and discharges the described outlet of heat transferring medium, and described outlet runs through described catalyst and stretches out described reactor shell 1.
Described in adjacent two groups, circular thermofin pipe 2 is crisscross arranged along reactor shell 1 axial direction, and described in two adjacent groups, between circular thermofin pipe 2, angle is 30～120°；The internal diameter of described circular thermofin pipe 2 is 25～100mm, and the distance between adjacent two described circular thermofin pipes 2 is 50～1000mm.
Heat is outwards given when course of reaction reaction bed temperature is higher than heat-transfer medium temperature, when reaction bed temperature is lower than heat-transfer medium temperature, by heat transfer medium by circular thermofin pipe 2 to beds heat supply, running can remaining, in reactor shell 1, temperature is > 250 DEG C, thus can effectively prevent the generation of hot hydrochloric acid.
For the clearer explanation present invention, by the described circular import of thermofin pipe 2 of different layers catalyst, outlet, heat transfer medium charging aperture label respectively in Fig. 1, heat transfer medium charging aperture on described thermofin pipe 2 in different catalysts bed is for being numbered 11a～33a from top to bottom, discharging opening is numbered 11b～33b, total valve is numbered v1～v3, heat transfer medium charging aperture valve is numbered v11～v33, and distributor charging aperture valve is numbered 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 certain beds, the heat transfer medium charging aperture valve v11～v33 of the corresponding bed of unlatching carrys out the flow of Heat Transfer Control medium and stablizes and improve the purpose of reaction efficiency to reach control temperature of reactor.
Preferably, supporting screening plate 3 is circular hole punching type plate, it is possible to good supporting catalyst, and ensures that reacting abundant continuation carries out downward or upward.The bottom of supporting screening plate 3 is side-fed distributor 4 immediately, and it is distributed the circular port having diameter to be 40～60mm.Side-fed distributor 4 bottom is provided with bracing ring 6 for ensureing supporting screening plate 3 and the stability of side-fed distributor 4.Owing to the catalytic performance of catalyst can be caused long lasting for reaction constantly to reduce from top to bottom, arranging multilamellar charging aperture and carry out multiple feed, its side-fed distributor 4 then carries out selectively unlocking according to concrete response situation by valve v14～v34.
The catalyst of this preparing chlorine by oxidizing hydrogen chloride can adopt with active A l2O3For carrier, Cu is active component, and lead, manganese etc. are the catalyst of coagent.
Especially, due to the lasting use of catalyst, its active component can be assembled to reactor exit under the continuous souring of gas phase flow media in reactor, catalyst is used and equipment runs and brings adverse effect.When catalysqt deactivation phenomenon goes out when to reactor middle and lower part, this invention takes the way of upper and lower charging order commutation, by lower discharge port B as material inlet, the upper feeding mouth A on reactor top is as discharging opening, and the charging of its side distributor charging aperture 14～34 is sequentially carried out unlatching according to catalysqt deactivation situation.
A kind of preparing chlorine by oxidizing hydrogen chloride novel reactor that the present invention relates to according to its use of embodiment and work process is:
Hydrogen chloride and oxygen feed gas are preheated to 300～350 DEG C, entered into by the upper feeding mouth A in such as Fig. 1 and in beds C1, carry out catalytic oxidation, reaction temperature is 350～420 DEG C, reaction is exothermic reaction, heat transferring medium is by removing the heat that reaction produces in time through the circular thermofin pipe 2 of bed, it is ensured that reacting balance carries out efficiently.The mixing gas such as end product chlorine, hydrogen chloride and steam flows out through low head, and ellipsoidal head place, bottom heat tracing coil pipe 5 valve is in normally open, and heat transfer medium enters from 5a, and 5b flows out, it is ensured that reactor lower part hydrops will not produce.
Along with the passage in response time, catalyst occurs inactivation to cause that reaction efficiency reduces from top to bottom.Alternative carries out side-fed this moment, and can be imported and exported by reactor and exchange, and carry out reverse charging, do so can high degree efficiently utilize catalyst, extend the service life of catalyst.
A kind of embodiment of the present invention:
Below, adopt embodiment that the present invention is described in more details, but the present invention is not limited by this embodiment.
As preparing chlorine by oxidizing hydrogen chloride novel reactor, using the reactor identical with shown in Fig. 1, this reactor shell axial length is 8000mm, and internal diameter is 1400mm, and material used is 304 rustless steels.Time different from Fig. 1, each layer of reactor equipped with temperature sensor to show bed temperature in time, it is ensured that efficiently carrying out of reaction.Additionally, beds is provided with hand hole up and down, it is used for facilitating the handling of catalyst.
The sieve plate that whole reactor is installed by centre is divided into 3 layers, and every layer of catalyst filling height is 1000mm, supporting screening plate 3 is provided with the circular port of 2mm for not affecting again passing through of product while ensureing catalyst and not falling out.Side-fed distributor, feed pipe internal diameter 50mm are installed bottom sieve plate, distributor uniformly has the circular port of 2mm.In each beds, average mark is furnished with 3 groups of transverse direction heat-exchange finned tubes, and bore is 32mm, and the axial distance of two adjacent groups thermofin pipe is 200mm, and 3 groups of finned tubes are 90 ° at the axial angle of reactor.It is designed with valve to control rate-of flow additionally, often organize on finned tube and feed distributor, bed is provided with multiple temperature sensor instruction bed temperature.Ellipse head place, bottom is provided with heat tracing pipe, it is prevented that have hydrops to accelerate reactor corrosion in course of reaction.
nullOpen the valve of the heat transfer coils of each layer beds，Temperature is about the conduction oil importing of 350 DEG C，Beds slowly heats up therewith，When temperature sensor displays temperature is about 320 DEG C，Close conduction oil entrance，The mixture (mass ratio of hydrogen chloride and oxygen is 2:1) of hydrogen chloride and oxygen that flow is about 2697kg/h is preheating to 300 DEG C，Enter into ground floor beds from reactor upper inlet A and carry out preparing chlorine by oxidizing hydrogen chloride reaction，Side feed opening is closed，Reaction conversion ratio is 80～90%，The hydrogen chloride that flow is about 187kg/h is obtained after reaction、The oxygen of 452kg/h、The chlorine of 1641kg/h and the steam of 417kg/h flow out from the lower part outlet B of reactor，Reaction keeps pressure to carry out under 0.3MPa，Now reaction bed temperature starts slow rising，It is again turned on conduction oil valve，The conduction oil that temperature is about 230～280 DEG C imports in heat exchange，Controlling opening of valve，Keep reaction temperature between 400～420 DEG C，Simultaneously，The conduction oil that temperature is 250 DEG C is passed into by the valve opening lower ellipse head heat tracing pipe，Ensure that end socket exit will not produce hydrops and accelerate corrosion.
Carrying out along with reaction, there is top-down slow inactivation in catalyst, reactor outlet raw material composition becomes the steam of the hydrogen chloride of 281kg/h, the oxygen of 472kg/h, the chlorine of 1550kg/h and 394kg/h, and reaction target product decreases, it was shown that catalyst the first bed inactivates.Now, close reactor upper feed inlet A, open the side-fed distributor that the second beds is provided with, mass flow and concentration remain unchanged and enter into the second beds from here, product composition becomes the steam of the hydrogen chloride of 235kg/h, the oxygen of 462kg/h, the chlorine of 1595kg/h and 405kg/h, showing that catalyst activity has had rising by a small margin, target product chlorine gas concentration increases.Same, along with reaction carries out, also there is slow inactivation in the second bed catalyst, now open the valve of third layer side-fed distributor, close second layer side-fed distributor valve, close material outlet B, open material inlet A, it is achieved import and export the exchange of position.Under this kind of condition, observe the concentration of chlorine in material outlet and start again the rising occurred by a small margin.
Carrying out along with reaction, each layer catalysqt deactivation is deepened, when reacting material outlet concentration reduces to the steam of the hydrogen chloride of 375kg/h, the oxygen of 493kg/h, the chlorine of 1458kg/h and 371kg/h, stopped reaction carries out the load again of catalyst activity component to recover its reactivity.Nitrogen is blown into from reactor upper feed inlet A, remain the valve opening of lower ellipse head heat tracing pipe, question response actuator temperature slowly drops to less than 60 DEG C, and when in outlet material, hydrogen chloride and chlorine gas concentration are not higher than 0.1%, open on each layer beds equipped with hand hole, by each layer catalyst take out carry out load again.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (10)
1. the novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas, it is characterized in that, including reactor shell, upper cover, low head, multiple supporting screening plate, multiple side-fed distributor and many groups for supplying or remove the heat exchanger tube of inside reactor heat
Described reactor shell is vertically arranged, and described reactor shell top is provided with described upper cover, is provided with described low head bottom it；Described upper cover is provided with the upper feeding mouth for passing into unstrpped gas, described low head is provided with the lower discharge port generating gas for discharging reaction,
Described supporting screening plate is horizontally fixed in described reactor cylinder body, described reactor shell is axially divided into multilamellar along described reactor shell by multiple described supporting screening plates, each described sieve plate is all filled with catalyst, every layer of described catalytic inner is provided with and organizes heat exchanger tube more, described heat exchanger tube is horizontally disposed with in the catalyst, and the described heat exchanger tube of many groups is axially evenly distributed in described catalyst along described reactor shell；Described side-fed distributor is horizontally fixed in described reactor cylinder body and is located close to the lower section of described supporting screening plate, described side-fed distributor is identical with described supporting screening plate number and one_to_one corresponding, the bottom of described side-fed distributor is fixed with annular brace circle, and described bracing ring is fixing with described reactor shell inwall to be connected.
2. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterized in that, described heat exchanger tube is provided with the outlet of the import and discharge heat transfer medium for the passing into heat transfer medium that are oppositely arranged on both sides, and described import and described outlet extend through described catalyst and stretch out outside described reactor shell；Described import department is provided with heat transfer medium imported valve, the described imported valve in every layer of described catalyst by after pipeline parallel connection by total valve control；The described total valve of each layer is connected in parallel by pipeline.
3. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 2, it is characterized in that, described heat exchanger tube is circular thermofin pipe, described circular thermofin pipe includes being oppositely arranged in the same plane and be positioned at the first circular arc fin pipeline of both sides, the second circular arc fin pipeline and multiple straight fins pipeline that is parallel to each other, and described straight fins pipeline is fixed between described first circular arc fin pipeline and the second circular arc fin pipeline；Described first circular arc fin pipeline and the size of the second circular arc fin pipeline, shape are identical, it is interconnected between described first circular arc fin pipeline, the second circular arc fin pipeline and multiple described straight fins pipeline, one end of described first circular arc fin pipeline is connected with described second circular arc fin pipeline by described straight fins pipeline, the other end of described first circular arc fin pipeline extends radially outward out composition and passes into the described import moving thermal medium, and described import runs through described catalyst and stretches out described reactor shell；One end of described second circular arc fin pipeline is connected with described first circular arc fin pipeline by described straight fins pipeline, the other end of described second circular arc fin pipeline extends radially outward out composition and discharges the described outlet of heat transferring medium, and described outlet runs through described catalyst and stretches out described reactor shell.
4. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 3, it is characterized in that, described in adjacent two groups, circular thermofin pipe is crisscross arranged along reactor shell axial direction, and described in two adjacent groups, between circular thermofin pipe, angle is 30～120 °；The internal diameter of described circular thermofin pipe is 25～100mm, and the distance between adjacent two described circular thermofin pipes is 50～1000mm.
5. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterized in that, described side-fed distributor includes main feed pipe and multiple straight tube being parallel to each other at grade, and described main feed pipe one end is provided with distributor charging aperture, and the other end seals；Described distributor charging aperture runs through described reactor shell and protruding, and described distributor charging aperture is provided with distributor charging aperture valve；Multiple described straight tubes are uniformly fixed on described main feed pipe towards the other end from one end of the described main feed seal of tube, the closed at both ends of described straight tube, and the middle part of described straight tube is fixed on described main feed pipe and is connected with described main feed pipe；Described straight tube place plane is parallel with described reactor shell cross section；Multiple equally distributed charging hole it is provided with bottom described straight tube；The end of multiple described straight tubes is each attached to the top of described bracing ring, described bracing ring be fixed on recklessly reactor shell medial wall on；Described side-fed distributor and described reactor shell inner shape match.
6. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 5, it is characterised in that the diameter of described charging hole is 0.5～20mm；The internal diameter of described straight tube is 20～100mm, and the distance between adjacent two described straight tubes is 50～500mm, and the length of described straight tube is 200～1800mm, and the length of centrally located described straight tube is the longest, and described straight tube gradually successively decreases to both sides from middle；Described main feed bore is 20～100mm, and its length is 800～2200mm.
7. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterized in that, heat tracing coil pipe is installed outside described low head, described heat tracing coil pipe spirals and is welded on outside described low head, described heat tracing coil pipe dish is provided with heat tracing feed pipe inlet and heat tracing pipe outlet, is filled with heat tracing medium in described heat tracing coil pipe；The internal diameter of described heat tracing coil pipe is 10～60mm.
8. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, it is characterized in that, described supporting screening plate bottom margin is fixed on inside described reactor shell by multiple right angles pad, described right angle pad is while being fixed on described supporting screening plate bottom margin, and its another side is fixed on inside described reactor shell；Described supporting screening plate is circular hole punched holes type plate, and the aperture of described circular hole is 0.2～20mm.
9. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to any one of claim 1 to 8, it is characterized in that, described supporting screening plate has 2～5, described side-fed distributor has 2～5, described heat exchanger tube has 6～25 groups, described reactor shell is axially divided into 2～5 layers along described reactor shell by described supporting screening plate, every layer of described catalytic inner is provided with 2～5 groups of heat exchanger tubes, described heat exchanger tube is horizontally disposed with in the catalyst, and described in 2～5 groups, heat exchanger tube is axially evenly distributed in described catalyst along described reactor shell；The internal diameter of described reactor shell is 500mm～2000mm, and its axial height is 4500mm～18000mm；The height of described catalyst is 500mm～1500mm.
10. a kind of novel fixed bed reactors of catalytic oxidation of hydrogen chloride for preparing chlorine gas according to any one of claim 1 to 8, it is characterised in that the axial distance of described side-fed distributor and catalyst is 400～1000mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117580A (en) * | 2017-03-31 | 2017-09-01 | 万华化学集团股份有限公司 | A kind of use trickle bed reactor carries out the method that chloration hydro-oxidation 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 |
| CN109289713A (en) * | 2018-10-18 | 2019-02-01 | 辽宁石油化工大学 | A kind of mosquito-repellent incense coil pipe isothermal reactor and application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687160A (en) * | 2007-07-13 | 2010-03-31 | 拜尔技术服务有限责任公司 | The method for preparing chlorine by multi step adiabatic gas phase oxidation |
| CN103420340A (en) * | 2003-12-23 | 2013-12-04 | 巴斯夫欧洲公司 | Method for the production of chlorine by means of gas phase oxidation of hydrogen chloride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420340A (en) * | 2003-12-23 | 2013-12-04 | 巴斯夫欧洲公司 | Method for the production of chlorine by means of gas phase oxidation of hydrogen chloride |
| CN101687160A (en) * | 2007-07-13 | 2010-03-31 | 拜尔技术服务有限责任公司 | The method for preparing chlorine by multi step adiabatic gas phase oxidation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117580A (en) * | 2017-03-31 | 2017-09-01 | 万华化学集团股份有限公司 | A kind of use trickle bed reactor carries out the method that chloration hydro-oxidation prepares chlorine |
| 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 |
| CN109289713A (en) * | 2018-10-18 | 2019-02-01 | 辽宁石油化工大学 | A kind of mosquito-repellent incense coil pipe isothermal reactor and application method |
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