CN105617946A - Moving bed radial flow reactor and application thereof - Google Patents
Moving bed radial flow reactor and application thereof Download PDFInfo
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Abstract
A moving bed radial flow reactor and an application thereof are provided. The reactor is divided into a fluid feed channel, a catalyst fixed bed layer, a catalyst moving bed layer and a fluid discharge channel in the radial direction from outside to inside or from inside to outside; the top and the bottom of the reactor are respectively provided with a fluid feed inlet and a fluid discharge outlet; the fluid feed inlet communicates with the fluid feed channel; the fluid discharge channel communicates with the fluid discharge outlet; the top of the catalyst moving bed layer is provided with a moving bed catalyst inlet, and the bottom of the catalyst moving bed layer is provided with a moving bed catalyst outlet; the fluid feed channel, the catalyst fixed bed layer, the catalyst moving bed layer and the fluid discharge channel are separated by materials with pores, and the pore size can meet the case that gas can pass through the pores while catalyst particles cannot pass through the pores. The moving bed radial flow reactor provided by the invention is suitable for a chemical reaction process of two catalysts having synergistic effect and having different inactivation speeds.
Description
Technical field
The present invention relates to the reactor of a kind of chemical field and application thereof, more particularly, it relates to a kind of moving bed radial flow reactor for chemical process strengthening and application thereof.
Technical background
Process intensification refers to and is producing and using new technique and new equipment in the course of processing, it is achieved the Optimum Matching between the process factors such as course of reaction and heat transfer, mass transfer and concentration, thus improving energy efficiency, increasing equipment capacity, reducing waste discharge. Chemical process strengthening is the target of domestic and international chemical circles long-term struggle, more causes the attention of people in recent years. In many developed countries such as the U.S., chemical process strengthening is listed in one of three big fields that current Chemical Engineering first develops.
Relating to Various Complex reaction in chemical reaction process, and some reaction is for reversible reaction, production concentration affects balancing response, for strengthening course of reaction, it is necessary to introduce physically or chemically that means are to reduce some reactant concentration, with this enhancement purpose product yield. When realizing these process intensification means, it is necessary to corresponding reactor matches enforcement.
US7501111B2 proposes a kind of for SO2And H2S is converted into tubular type claus catalytic reaction device (radial flow reactors) of sulfur and water, comprises sulfur separator, at least one concentric tubular reactor (radial reactor) and annular condensing zone (heat exchange medium flow region). Sulfur separator comprises reaction gas, Process Gas passage and at least one molten sulfur entrance. Process Gas passage is provided with outlet, and temperature-controlled area comprises the gateway of heat exchange medium. Reactor is between Process Gas passage and reactant gas passage. Reactor comprises ring-type catalytic reaction zone, next-door neighbour's reactant gas passage and condensing zone. Condenser and radial flow reactors are coupled together by reactor, enhance course of reaction.
CN1150331C proposes a kind of moving bed radial reactor, including a housing, housing is by circular side wall, upper cover and bottom bulkhead composition, the Intranet and outer net that are axially sequentially arranged from inside to outside along housing it is provided with in housing, annular space is formed between Intranet and outer net, housing is provided with reactant entrance, reactant exports, top end socket is provided with catalyst ingress pipe, bottom bulkhead is provided with catalyst exit line, catalyst ingress pipe is connected with annular space space with discharge pipe, catalyst exit line forms opening on the inner surface of bottom bulkhead, it is characterized in that: be provided with skirt in the bottom of Intranet, the outer surface of skirt has top to bottm to tilt along in-house network to the direction of outer net, its upper limb is connected with Intranet, the radial position of lower edge is positioned at the inner side of the radial position of described catalyst exit line.
US7125529B2 proposes a kind of Radial Flow reactor with two kinds of beds. Reactor includes outlet, entrance, three coaxial central canals, the first beds, the second beds. The annular space that reactor outer wall and outermost central canal are constituted is fluid tapping channel, and is connected with Reactor inlet; The annular space district that outermost central canal and central canal placed in the middle are constituted is the first bed district, and the annular space district that central canal placed in the middle and interior central canal are constituted is the second bed district, and the region that central canal surrounds is fluid passage, and is connected with reactor outlet. Each central canal allows fluid from, and stops catalyst to pass through. This reactor only adapts to the process that catalyst activity is constant.
US8101133B2 proposes a kind of radial flow reactors, and the beds of reactor is two-layer beds, and the physical property of every layer of catalyst is different. The reaction of this radial flow can only catalyst activity is constant in adjustment reaction process course of reaction, it is impossible to adapt to the course of reaction that catalyst slowly inactivates.
In the course of reaction of some complexity, the different types of catalyst of reaction needed, catalyst activity is not affected by partial reaction, and partial reaction can cause catalysqt deactivation, and the catalyst of inactivation needs regeneration. If these courses of reaction are separately performed, then non-deactivated catalyst avoids the need for regeneration. Carrying out once these courses of reaction be coupled, traditional reactor can not meet this course of reaction, all catalyst certainly will be caused all to regenerate, cause the waste of the energy.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide the moving bed radial flow reactor of a kind of process intensification, can load two kinds of catalyst of different nature. The two of the technical problem to be solved in the present invention are to provide the application process of above-mentioned moving bed radial flow reactor.
A kind of moving bed radial flow reactor, reactor radially ecto-entad or be divided into fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel from inside to outside; Reactor head and bottom are respectively provided with fluid feed mouth and fluid discharging opening; Described fluid feed mouth communicates with fluid feed path, and described fluid discharging opening communicates with fluid tapping channel; Moving-bed of catalyst layer top arranges movable bed catalyst import, bottom arranges movable bed catalyst outlet; Between described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel, the material through having hole separates, and pore size meets gas can be passed through, and catalyst granules cannot pass through.
Preferably, it is provided with demarcation strip in fluid feed path, catalyst fixed bed layer and fluid tapping channel, in order to change fluid radial flow direction between fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel so that fluid passes in and out two beds back and forth. Under the barrier effect of demarcation strip, the fluid entering fluid feed path enters fluid tapping channel by catalyst fixed bed layer and moving-bed of catalyst layer, then fluid change direction enters moving-bed of catalyst layer and catalyst fixed bed layer from fluid tapping channel, arrive fluid feed path, when installing multiple demarcation strip, fluid frequently changes radial flow direction, eventually through fluid discharging opening outflow reactor.
A kind of application process of moving bed radial flow reactor, adopt above-mentioned moving bed radial flow reactor, adopt two kinds and there is synergistic catalyst, the first catalyst of not easy in inactivation is added in catalyst fixed bed layer, the second catalyst of easy in inactivation adds moving-bed of catalyst layer by movable bed catalyst import, reaction raw materials is entered fluid feed path by fluid feed mouth, pass radially through catalyst fixed bed layer and moving-bed of catalyst layer again, under the effect of two kinds of catalyst, reaction raw materials generation chemical reaction generates product, the second catalyst in moving-bed of catalyst layer inactivates gradually, and remove reactor gradually downward, after entering regenerator regeneration, return catalizer moves bed and recycles, reaction mixture gas body through catalyst fixed bed layer and moving-bed of catalyst layer enters fluid tapping channel, again through fluid discharging opening outflow reactor, enters follow-up piece-rate system.
Having the beneficial effect that of moving bed radial flow reactor provided by the invention and application process thereof
Fixing bed provided by the invention-moving bed coupling bed reactor arranges two kinds of beds, the reaction that the applicable catalyst activity of catalyst fixed bed layer does not change substantially; The reaction that the applicable catalyst of moving-bed of catalyst layer slowly inactivates. Adopt moving bed radial flow reactor provided by the invention can meet a part of catalyst activity in course of reaction constant, without regeneration, another part catalyst needs removal reactor to go regeneration because slowly inactivating, the requirement that two reactors could meet course of reaction is adopted to become adopting a reactor can meet requirement by needing, simplify response system, reduce running cost.
Accompanying drawing explanation
Fig. 1 is the first embodiment structural representation of moving bed radial flow reactor;
Fig. 2 is the top view of moving bed radial flow reactor main part;
Fig. 3 is moving bed radial flow reactor the second embodiment structural representation;
Fig. 4 is the third embodiment structural representation of moving bed radial flow reactor;
Fig. 5 is the 4th kind of embodiment structural representation of moving bed radial flow reactor;
Fig. 6 is the 5th kind of embodiment structural representation of moving bed radial flow reactor;
Fig. 7 is the 6th kind of embodiment structural representation of moving bed radial flow reactor;
Fig. 8 is the 7th kind of embodiment structural representation of moving bed radial flow reactor;
Fig. 9 is the 8th kind of embodiment structural representation of moving bed radial flow reactor.
Detailed description of the invention
Radial flow moving-burden bed reactor provided by the invention is so embodied as. The top of the container mentioned in description refers to the position of the 90%-100% of container height from the bottom to top, and the bottom of the container mentioned refers to the position of the 0-10% of container height from the bottom to top.
A kind of moving bed radial flow reactor, reactor radially ecto-entad or be divided into fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel from inside to outside; Reactor head and bottom are respectively provided with fluid feed mouth and fluid discharging opening; Described fluid feed mouth communicates with fluid feed path, and described fluid discharging opening communicates with fluid tapping channel; Moving-bed of catalyst layer top arranges movable bed catalyst import, bottom arranges movable bed catalyst outlet; Between described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel, the material through having hole separates, and pore size meets gas can be passed through, and catalyst granules cannot pass through.
In moving bed radial flow reactor provided by the invention, reactor shell upper and lower side connects upper low head, and end socket is provided with fluid feed inlet and outlet and movable bed catalyst is imported and exported. Described fluid feed path is connected with fluid feed mouth, and described fluid tapping channel is connected with fluid discharging opening. Described movable bed catalyst is imported and exported and is connected with movable bed catalyst bed.
Preferably, it is provided with demarcation strip in catalyst fixed bed layer, fluid feed path and fluid tapping channel, in order to change fluid radial flow direction between fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel so that fluid passes in and out two beds back and forth. Under the barrier effect of demarcation strip, the fluid entering fluid feed path enters fluid tapping channel by catalyst fixed bed layer and moving-bed of catalyst layer, then fluid change direction enters moving-bed of catalyst layer and catalyst fixed bed layer from fluid tapping channel, arrive fluid feed path, fluid frequently changes radial flow direction, eventually through fluid discharging opening outflow reactor.
The quantity of described demarcation strip is at least above 1, and the demarcation strip of the demarcation strip in catalyst fixed bed layer and fluid feed path is presented axially in same sectional position. Demarcation strip can be horizontal plate, it is also possible to for having disk ring baffle plate or the herringbone baffle plate at certain inclination angle. The demarcation strip of fluid feed path and fluid tapping channel is spaced apart on axial location.
In moving bed radial flow reactor provided by the invention, the ratio of the sectional area of described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel is 1:(2-12): (2-10): (0.1-1), under preferable case, the ratio of the sectional area of described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel is 1:(3-9): (2-6): (0.2-0.8).
The application process of moving bed radial flow reactor provided by the invention, adopt moving bed radial flow reactor provided by the invention, adopt two kinds and there is synergistic catalyst, the first catalyst of not easy in inactivation is added in catalyst fixed bed layer, the second catalyst of easy in inactivation adds moving-bed of catalyst layer by movable bed catalyst import, reaction raw materials is entered fluid feed path by fluid feed mouth, pass radially through catalyst fixed bed layer and moving-bed of catalyst layer again, under the effect of two kinds of catalyst, reaction raw materials generation chemical reaction generates product, the second catalyst in moving-bed of catalyst layer inactivates gradually, and remove reactor gradually downward, after entering regenerator regeneration, return catalizer moves bed and recycles, reaction mixture gas body through catalyst fixed bed layer and moving-bed of catalyst layer enters fluid tapping channel, again through fluid discharging opening outflow reactor, enters follow-up piece-rate system.
Moving bed radial flow reactor provided by the invention can be used for petroleum hydrocarbon desulfurizing method by adsorption, adopt two kinds and there is synergistic catalyst, the Hydrobon catalyst of not easy in inactivation is added in catalyst fixed bed layer, the desulfuration adsorbent of easy in inactivation adds moving-bed of catalyst layer by movable bed catalyst import, petroleum hydrocarbon is entered fluid feed path with hydrogen by fluid feed mouth, passing radially through catalyst fixed bed layer and moving-bed of catalyst layer again, the sulfur-bearing hydrocarbon molecule in petroleum hydrocarbon generates H with hydrogen reaction2S, H2S is chemically adsorbed on desulfuration adsorbent, and the desulfuration adsorbent in moving-bed of catalyst layer inactivates gradually, down through movable bed catalyst outlet removal reactor, returns and recycle in entrance adsorbent regenerator after regeneration; Reaction mixture gas body through catalyst fixed bed layer and moving-bed of catalyst layer enters fluid tapping channel, through fluid discharging opening outflow reactor, obtains the petroleum hydrocarbon product after desulfurization.
Described Hydrobon catalyst is the catalyst of one or more the metal active constituent elements on heat-resistant inorganic oxide in load Ni, Co and W, and its metal active constituent element can be 0 valence state metal, it is also possible to for metal sulfide. Described heat-resistant inorganic oxide is selected from aluminium oxide and/or silicon oxide. Heretofore described Hydrobon catalyst adopts customary preparation methods to prepare, for instance can with Kaolin for substrate, and with Alumina gel for binding agent, after being through impregnation with a certain amount of hydrogenation activity constituent element, roasting prepares.
Described desulfuration adsorbent is commonly used in the art have absorption H2The material of S function, is generally made up of active component and substrate. The mixture of one or more that described active component is selected from copper oxide, zinc oxide, ferrum oxide, manganese oxide and calcium oxide, it is preferable that the mixture of one or more in zinc oxide, ferrum oxide and calcium oxide. Described substrate is heat-resistant inorganic oxide, it is preferable that the mixture of one or more in aluminium oxide, titanium oxide and zirconium oxide.
The preparation method of described desulfuration adsorbent is this area conventional method, it does not have special requirement. Such as with Kaolin for substrate, with Alumina gel and or Ludox for binding agent, add a certain proportion of H2S adsorption activity constituent element, prepares through making beating, mist projection granulating, roasting.
The grain graininess of described desulfuration adsorbent is conventional selection, is as the criterion being capable of flowing. Usually, the grain graininess of described desulfuration adsorbent is 20 microns��30 millimeters, it is preferable that 50 microns��10 millimeters, more preferably 100 microns��5 millimeters. The grain graininess of Hydrobon catalyst and desulfuration adsorbent is volume average particle sizes, it is possible to adopt laser particle size analyzer to measure.
The scope of the boiling range of described petroleum hydrocarbon is selected from C 4 fraction��220 DEG C. The described petroleum hydrocarbon one or more mixture in C 4 fraction, direct steaming gasoline, catalytic gasoline and coker gasoline.
The operating condition of described moving bed radial flow reactor is: described reaction temperature is 200��600 DEG C, it is preferable that 250��500 DEG C; Reaction pressure is 0.4��10MPa, it is preferable that 1.0��8MPa; Weight (hourly) space velocity (WHSV) is 0.1��50h-1, it is preferable that 0.2��40h-1. The consumption of described hydrogen is the conventional selection of this area. Usually, in charging, the volume ratio of hydrogen and petroleum hydrocarbon is 0.05��5Nm3/m3, it is preferred to 0.1��4.5Nm3/m3, more preferably 0.2��4Nm3/m3��
Described moving-bed of catalyst pull-up sulfur absorbent translational speed in moving-burden bed reactor is 0.02��1.0m/h, it is preferable that 0.05��0.5m/h.
Described petroleum hydrocarbon raw material is preferably performed preheating before entering the reactor, and preheating temperature is 120��500 DEG C, more preferably 150��400 DEG C. Petroleum hydrocarbon and the mixture of hydrogen after preheating first pass through fluid feed mouth and enter in fluid feed path, then enter catalyst fixed bed layer in the way of radial flow, and raw material contacts with Hydrobon catalyst and realizes desulphurization reaction. H is generated with hydrogen reaction at catalyst fixed bed layer Petroleum Hydrocarbon2S, reaction mixture gas body enters moving-bed of catalyst layer with radial flow fashion, contacts with the desulfuration adsorbent in moving-bed of catalyst layer, H2S is chemisorbed load on desulfuration adsorbent. Along with reaction carries out, desulfuration adsorbent inactivates gradually and passes downwardly through movable bed catalyst outlet removal reactor along moving-bed of catalyst layer. In adsorbent regenerator, the desulfuration adsorbent of high temperature regeneration enters in moving-bed of catalyst layer through movable bed catalyst import and recycles. Reaction mixture gas body through catalyst fixed bed layer and moving-bed of catalyst layer enters fluid tapping channel, obtains the petroleum hydrocarbon fraction after desulfurization again through fluid discharging opening outflow reactor.
Illustrate the implementation of the present invention referring to accompanying drawing, but the present invention is not therefore subject to any restriction.
Accompanying drawing 1 is the first embodiment of moving bed radial flow reactor, and accompanying drawing 2 is the reactor body top partial view diagram of the first embodiment. As shown in accompanying drawing 1, accompanying drawing 2, reactor body is made up of vertical type cylinder shape housing 7, upper cover 13, low head 20, and described upper cover 13 and low head 20 can be spherical, elliposoidal or flat board. Reactor body is radially from inside to outside for the pipe of concentric: interior pipe 10, intervalve 9, outer tube 8, housing 7 are constituted. Interior pipe 10, intervalve 9 and outer tube 8 can for the standpipes of the tube of silk screen composition or perforate, and silk screen gap and hole size to meet gas can be passed through, and catalyst granules cannot pass through. The annular space region that the tube wall of said inner tube 10 and intervalve 9 is defined is catalyst fixed bed layer 4, and the defined annular space region of the tube wall of intervalve 9 and outer tube 8 is moving-bed of catalyst layer 5. Interior pipe 10 area defined is fluid feed path 3, and the annular space region that the tube wall of housing 7 and outer tube 8 is constituted is fluid tapping channel 6. Fluid feed path 3, catalyst fixed bed layer 4, moving-bed of catalyst layer 5 and fluid tapping channel 6 radially it is followed successively by from inside to outside in housing. Catalyst transfixion in catalyst fixed bed layer; Moving-bed of catalyst layer 5 top is provided with movable bed catalyst import 11, bottom is provided with movable bed catalyst outlet 2, in catalyst bed mobile layer district, catalyst can be entered by movable bed catalyst import 11 continuously from top to bottom, then passes through movable bed catalyst outlet 2 outflow. Fluid feed path 3 is connected with fluid feed mouth 1, and fluid tapping channel 6 is connected with fluid discharging opening 12.
Can welding bottom interior pipe 10, intervalve 9 and outer tube 8 in the gripper shoe 19 of bottom, top is connected with fixed support plate. Fluid feed path 3 top seals, and fluid can not pass through, and can weld blind plate by interior pipe top and realize in engineering. Catalyst fixed bed layer 4 top is provided with catalyst dress agent mouth, and bottom is provided with catalyst unloading mouth (not marking and drawing in figure).
Being provided with demarcation strip 14��18 in catalyst fixed bed floor district 4, fluid feed path 3 and fluid tapping channel 6, wherein the demarcation strip of catalyst fixed bed layer 4 and fluid feed path 3 is located axially at identical height at interior pipe 10. The demarcation strip of fluid feed path 3 and fluid tapping channel 6 is spaced apart on axial location. The effect of demarcation strip is to change fluid through the order of two beds, strengthens course of reaction with this. Demarcation strip is by welding or other method connects with corresponding tube wall, and it is that Catalyst packing at respective regions well welds again that the demarcation strip in beds is connected with corresponding tube wall, or demarcation strip is provided with and fills agent pipeline and shut after Catalyst packing.
Reactor working condition shown in Fig. 1 is such that adding in catalyst fixed bed layer by the catalyst of not easy in inactivation, the catalyst of easy in inactivation adds moving-bed of catalyst layer 5 by catalyst inlet 11, reacting gas is entered fluid feed path 3 by fluid feed mouth 1, under the barrier effect of demarcation strip 18, catalyst fixed bed layer 4 and mobile bed 5 is entered by fluid feed path 3, under the effect of two kinds of catalyst, reacting gas generation chemical reaction generates product. Reaction gas flow through moving-bed of catalyst layer 5 enters fluid tapping channel 6, under the effect of demarcation strip 17, fluid enters in catalyst fixed bed layer 4 then through moving-bed of catalyst layer 5 and reacts, reacted mixing gas enters fluid feed path, flows by action body at demarcation strip passes in and out two beds through frequent, promote the carrying out of reaction, improve purpose product yield. Catalyst in moving-bed of catalyst layer 5 inactivates gradually, and removes reactor gradually downward, enters regenerator and regenerates, and regenerated catalyst return catalizer moves bed 5 and realizes recycling of catalyst. Reaction mixture gas body is finally pooled together by fluid discharging opening 12 outflow reactor by fluid tapping channel, enters follow-up piece-rate system.
Accompanying drawing 3 is the second embodiment structural representation of moving bed radial flow reactor, and shown in Fig. 1, reactor is distinctive in that, fluid feed mouth is located on housing upper cover 13, and fluid discharging opening is located on housing bottom (head) 20.
Accompanying drawing 4 is the third embodiment structural representation of moving bed radial flow reactor, and shown in Fig. 1, the first embodiment is distinctive in that: the structure of catalyst reactor fixed bed and the diametrically opposed position of moving-bed of catalyst layer and the first the embodiment reactor shown in Fig. 1 is contrary. The annular space region 6 that the tube wall of housing 7 and outer tube 8 is constituted is fluid feed path, and interior pipe 10 area defined 3 is fluid tapping channel. The annular space region 5 that the tube wall of intervalve 9 and outer tube 8 is defined is catalyst fixed bed layer, and the annular space region 4 that the tube wall of interior pipe 10 and intervalve 9 is defined is moving-bed of catalyst layer.
Accompanying drawing 5 is the 4th kind of embodiment structural representation of moving bed radial flow reactor, and shown in Fig. 4, the third embodiment is distinctive in that: fluid feed mouth is located on housing upper cover 13, and fluid discharging opening is located on housing bottom (head) 20.
Eight kinds of embodiment structural representations of the 5th kind of-of accompanying drawing 6-accompanying drawing 9 respectively moving bed radial flow reactor, and reactor shown in accompanying drawing 1-accompanying drawing 5 is distinctive in that, is not provided with demarcation strip in reactor.
The relative change of moving bed radial flow reactor inner catalyst fixed bed provided by the invention and moving-bed of catalyst layer relative position diametrically and fluid feed path and tapping channel can freely form the type of reactor of different structure, literary composition is not enumerated completely, but not thereby limiting the invention.
Moving bed radial flow reactor provided by the invention and application process thereof will be further described by the following examples, but not thereby limiting the invention.
In embodiment: yanshan petrochemical company limited taken from by liquefied gas raw material and catalytically cracked gasoline, its character is respectively in Table 1, table 2. Hydrobon catalyst is the Hydrobon catalyst RSDS-21 that catalyst branch company of Sinopec Group produces.
Desulfuration adsorbent is adopted and is prepared with the following method:
By 4.8Kg boehmite, (Shandong Aluminum Plant produces, Al2O3Content 62.0 weight %), the ZnO of 7Kg (Beijing North fine chemicals company limited, chemical pure) and the mixing making beating of 22.8Kg water, add 600g hydrochloric acid (concentration 36 weight %, Beijing North fine chemicals company limited, chemically pure reagent), by the granule that gained colloid spray drying forming is 1 mm in size, obtain micro-spherical catalyst Cat1 in 550 DEG C of roasting 2h afterwards. In like manner obtaining catalyst Cat2, Cat3 and Cat4, its composition is referring to table 3.
Table 1
| Liquefied gas forms, v% | |
| Propane | 42.64 |
| Propylene | 18.64 |
| Butane | 21.18 |
| Just, isobutene. | 14.2 |
| Butene-2 | 3.16 |
| C5+ | 0.18 |
| Sulfur content, ppm | 450 |
Table 2
| Gasoline stocks character | |
| Density (20 DEG C), kg/m3 | 726.5 |
| Sulfur content, ppm | 700 |
| Alkene, wt% | 37.5 |
| Aromatic hydrocarbons, wt% | 23.7 |
| Alkane, wt% | 38.8 |
Table 3
| Catalyst | Zinc oxide, wt% | Aluminium oxide, wt% | Titanium oxide, wt% | Zirconium oxide, wt% |
| Cat-1 | 70 | 30 | 0 | 0 |
| Cat-2 | 50 | 25 | 25 | 0 |
| Cat-3 | 45 | 30 | 0 | 25 |
| Cat-4 | 45 | 20 | 15 | 20 |
Embodiment 1-4 illustrates the effect adopting moving bed radial flow reactor provided by the invention for gasoline desulfurization.
Embodiment 1
Adopting radial flow moving-burden bed reactor as shown in Figure 1, the raw material of employing is catalytically cracked gasoline, and pressure is the mol ratio 0.3 of 3.0MPa, hydrogen and gasoline, reaction temperature 410 DEG C, reaction weight space velocity 4h-1, and desulfuration adsorbent regeneration temperature is 550 DEG C. Catalyst fixed bed layer filling Hydrobon catalyst RSDS-21, moving-bed of catalyst layer adopts desulfuration adsorbent Cat-1. Product property, operating condition and hydrogen consumption are as shown in table 4.
Embodiment 2
Adopting radial flow moving-burden bed reactor as shown in Figure 2, adopt catalytically cracked gasoline raw material in the same manner as in Example 1, catalyst fixed bed layer filling Hydrobon catalyst RSDS-21, moving-bed of catalyst layer adopts desulfuration adsorbent Cat-2. The pressure of radial flow moving-burden bed reactor is 2MPa, hydrogen and gasoline mol ratio 0.5, reaction temperature 440 DEG C, and adsorbent reactivation temperature is 550 DEG C. Product property, operating condition and hydrogen consumption are as shown in table 4.
Embodiment 3
Adopting radial flow moving-burden bed reactor as shown in Figure 3, the catalytically cracked gasoline that the raw material of employing is identical with embodiment example 1, catalyst fixed bed layer filling Hydrobon catalyst RSDS-21, moving-bed of catalyst layer adopts desulfuration adsorbent Cat-3. The pressure of radial flow moving-burden bed reactor is 4MPa, hydrogen and gasoline mol ratio 0.15, reaction temperature 350 DEG C, adsorbent reactivation temperature 550 DEG C. Product property, operating condition and hydrogen consumption are as shown in table 4.
Embodiment 4
Adopting radial flow moving-burden bed reactor as shown in Figure 4, adopting FCC gasoline in the same manner as in Example 1 is raw material, and catalyst fixed bed layer filling Hydrobon catalyst RSDS-21, moving-bed of catalyst layer adopts desulfuration adsorbent Cat-4. The pressure of radial flow moving-burden bed reactor is 1.5MPa, and hydrogen and gasoline feeding volume ratio are 0.25, reaction temperature is 480 DEG C, adsorbent reactivation temperature 550 DEG C. Product property, operating condition and hydrogen consumption are as shown in table 4.
Table 4
By the data of table 4 it can be seen that the sulfur content that can effectively reduce according to described method provided by the invention in gasoline, octane number loss simultaneously is less, decreases hydrogen consumption, reduces energy consumption.
Comparative example 1
Comparative example 1 illustrates for illustrating to adopt the Mcorx sulfur method desulfurized effect to liquefied gas.
The sulfur content of liquefied gas is 450ppm, and alkene mass content is 36%. Adopting tradition Mcorx deodorizing technology flow process to desulfuration of liquefied gas, product property is as shown in table 5.
Comparative example 2
Comparative example 2 illustrates to be used for illustrating that employing has hydrodesulfurization and the absorption bifunctional composite catalyst of sulfur to desulfuration of liquefied gas effect.
The preparation method of the composite catalyst in comparative example 2: the preparation referenced patent CN102343249B of composite catalyst, a certain amount of Zinc oxide powder (Headhorse company, purity 99.7wt.%) add the alumina hydrosol of solid content 10%, mixing carries out spray drying, calcining prepares 70 ��m of granules of particle diameter, then Nickelous nitrate hexahydrate (Beijing chemical reagents corporation is adopted, purity is more than 98.5%) granule of preparation carries out dipping and obtains catalyst by aqueous solution, wherein zinc oxide content 51wt%, nickel (calculates) content 16wt% with metallic nickel, all the other are aluminium oxide.
Adopt the liquefied gas raw material in comparative example 1. Adopt fluidized-bed reactor and fluid bed regenerator that catalytic cracking blau gas is carried out hydrodesulfurization. Reaction temperature is 350 DEG C, and pressure is the volume ratio of 1.5mPa, hydrogen and liquefied gas is 0.2Nm3/m3, reaction volume air speed is 4h-1, adsorbent composite catalyst regeneration temperature is 500 DEG C, and product property, operating condition and hydrogen consumption are as shown in table 5.
Embodiment 5
Desulfuration of liquefied gas reactor adopts type of reactor shown in Fig. 6. Adopt the raw material in comparative example 1. Fixed bde catalyst is catalyst RSDS-21. Catalyst after sulfuration is positioned in the catalyst fixed bed layer in reactor. After the desulfuration adsorbent Cat-1 prepared is processed in regenerator, it is transported in the moving-bed of catalyst layer in reactor. Passing into liquefied gas in reactor and hydrogen carries out desulphurization reaction, the desulfuration adsorbent removal reactor of inactivation enters regenerator and regenerates, and recycles. Adopt the raw material in comparative example 1. Product property, operating condition and hydrogen consumption are as shown in table 5.
Embodiment 6
Desulfuration of liquefied gas reactor adopts type of reactor as shown in Figure 7. In catalyst fixed bed layer, the desulphurization catalyst agent of filling is with embodiment 5. Desulfuration adsorbent is Cat-2, after processing, is transported to the moving-bed of catalyst layer in reactor in regenerator. Passing into liquefied gas in reactor and hydrogen carries out desulphurization reaction, the adsorbent removal reactor of inactivation enters regenerator and regenerates, and recycles. Product property, operating condition and hydrogen consumption are as shown in table 5.
Embodiment 7
Liquefaction stone desulfurization reactor adopts type of reactor as shown in Figure 8. In catalyst fixed bed layer, the desulphurization catalyst of filling is with embodiment 5. Desulfuration adsorbent in moving-bed of catalyst layer is Cat-3, after desulfuration adsorbent processes in regenerator, is transported in the moving-bed of catalyst layer in reactor. Passing into liquefied gas in reactor and hydrogen carries out desulphurization reaction, the desulfuration adsorbent removal reactor of inactivation enters regenerator and regenerates, and recycles. Product property, operating condition and hydrogen consumption are as shown in table 5.
Embodiment 8
Desulfuration of liquefied gas reactor adopts type of reactor as shown in Figure 9. The desulphurization catalyst agent of catalyst fixed bed layer filling is with embodiment 5. The desulfuration adsorbent of moving-bed of catalyst layer is Cat-4, after processing, is transported in the moving-bed of catalyst layer in reactor in regenerator. Passing into liquefied gas in reactor and hydrogen carries out desulphurization reaction, the desulfuration adsorbent removal reactor of inactivation enters regenerator and regenerates, and recycles. Product property, operating condition and hydrogen consumption are as shown in table 5.
Table 5
By the data of table 5 it can be seen that the sulfur content that can effectively reduce according to described method provided by the invention in blau gas, liquefied gas olefin loss is less simultaneously, decreases hydrogen consumption and energy consumption.
Claims (7)
1. a moving bed radial flow reactor, it is characterised in that reactor radially ecto-entad or be divided into fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel from inside to outside; Reactor head and bottom are respectively provided with fluid feed mouth and fluid discharging opening; Described fluid feed mouth communicates with fluid feed path, and described fluid discharging opening communicates with fluid tapping channel; Moving-bed of catalyst layer top arranges movable bed catalyst import, bottom arranges movable bed catalyst outlet; Between described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel, the material through having hole separates, and pore size meets gas can be passed through, and catalyst granules cannot pass through.
2. according to the moving bed radial flow reactor of claim 1, it is characterized in that, it is provided with demarcation strip in described fluid feed path, described catalyst fixed bed layer and described fluid tapping channel, in order to change fluid radial flow direction between fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel, fluid is made to pass in and out two beds back and forth, finally through fluid tapping channel outflow reactor.
3. according to the moving bed radial flow reactor of claim 1 or 2, it is characterized in that, the ratio of the sectional area of described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel is 1:(2-12): (2-10): (0.1-1).
4. according to the moving bed radial flow reactor of claim 3, it is characterized in that, the ratio of the sectional area of described fluid feed path, catalyst fixed bed layer, moving-bed of catalyst layer and fluid tapping channel is 1:(3-9): (2-6): (0.2-0.8).
5., according to the moving bed radial flow reactor of claim 1 or 2, it is characterised in that reactor shell upper and lower side connects upper low head, end socket is provided with fluid feed mouth, fluid discharging opening, movable bed catalyst import, movable bed catalyst outlet.
6. the application process of a moving bed radial flow reactor, it is characterized in that, adopt any one the moving bed radial flow reactor in claim 1-5, adopt two kinds and there is synergistic catalyst, the first catalyst of not easy in inactivation is added in catalyst fixed bed layer, the second catalyst of easy in inactivation adds moving-bed of catalyst layer by movable bed catalyst import, reaction raw materials is entered fluid feed path by fluid feed mouth, pass radially through catalyst fixed bed layer and moving-bed of catalyst layer again, under the effect of two kinds of catalyst, reaction raw materials generation chemical reaction generates product, the second catalyst in moving-bed of catalyst layer inactivates gradually, and remove reactor gradually downward, after entering regenerator regeneration, return catalizer moves bed and recycles, reaction mixture gas body through catalyst fixed bed layer and moving-bed of catalyst layer enters fluid tapping channel, again through fluid discharging opening outflow reactor, enters follow-up piece-rate system.
7. according to the application process of the moving bed radial flow reactor of claim 6, it is characterized in that, the described reaction mixture gas body through catalyst fixed bed layer and moving-bed of catalyst layer enters fluid tapping channel, under being arranged at the obstruct of demarcation strip of fluid tapping channel, enter in catalyst fixed bed layer then through moving-bed of catalyst layer and react, reaction mixture gas body enters back into fluid feed path, and under being arranged at the obstruct of demarcation strip of fluid feed path and catalyst fixed bed layer, fluid frequently passes in and out two beds.
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| CN110684551B (en) | 2021-10-08 |
| CN105617946B (en) | 2019-05-17 |
| CN110684551A (en) | 2020-01-14 |
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