CN203170305U - Combined-heat-exchange multi-shell-side fixed bed production equipment for preparing olefin from methanol - Google Patents
Combined-heat-exchange multi-shell-side fixed bed production equipment for preparing olefin from methanol Download PDFInfo
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- CN203170305U CN203170305U CN2012207434188U CN201220743418U CN203170305U CN 203170305 U CN203170305 U CN 203170305U CN 2012207434188 U CN2012207434188 U CN 2012207434188U CN 201220743418 U CN201220743418 U CN 201220743418U CN 203170305 U CN203170305 U CN 203170305U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Combined-heat-exchange multi-shell-side fixed bed production equipment for preparing olefin from methanol belongs to the technical field of olefin production and solves the technical problems that the conventional fixed bed reactor is complicated in reaction equipment and reaction heat transfer is difficult to control. The combined-heat-exchange multi-shell-side fixed bed production equipment for preparing the olefin from the methanol comprises a main reactor, wherein partition boards are installed between an upper tube plate and a lower tube plate of the main reactor to partition a cavity surrounded by the upper tube plate, the lower tube plate and a reactor body into 2-10 heat exchange shell sides which are not communicated with one another; the heat exchange shell sides comprise a first heat exchange shell side and the other heat exchange shell sides; tubes penetrate through the partition boards; and a cooling medium inlet/outlet is formed in the reactor body of each heat exchange shell side. Through the combined high-efficiency heat exchange, proportion of water steam in raw material gas and the load of a raw material gas heating furnace can be reduced.
Description
Technical field
The utility model relates to the technical field of being produced propylene and C4 alkene and gasoline by methyl alcohol or dimethyl ether, relates in particular to the production equipment of alkene such as a kind of diabatic, controllable temperature formula fixed bed reactors preparing propylene from methanol.
Background technology
Ethene, propylene are a kind of basic Organic Chemicals that is in great demand, and are mainly derived from petroleum refining process.Along with the scarcity day by day of petroleum resources, the technology that development is produced propylene by non-oil resources such as coal or natural gases more and more causes attention both domestic and external.Coal or natural gas preparing synthetic gas are ripe technologies by synthesis gas preparation methyl alcohol or dimethyl ether again.Therefore be the key technology of coal alkene processed from methyl alcohol or dimethyl ether production ethene, propylene.
Mainly being divided into 2 classes from the technology of methyl alcohol or dimethyl ether propylene processed, is the fixed bed MTP technology of purpose product based on the fluid bed MTO technology of alkene (ethene, propylene) with the propylene namely.MTP is preparing propylene from methanol technology, and principal product is propylene, by-product ethene, butylene, and gasoline etc., and MTO is methanol-to-olefins technology, and principal product is ethene and propylene, and the by-product butylene does not have gasoline substantially.The former is representative with the MTO technology of UOP/Hydro, Exxon-Mobil.MTO technology is catalyst with the SAPO-34 molecular sieve, and the reaction principal product is low-carbon alkenes such as ethene, propylene.By control operation temperature, and the prescription of catalyst etc., the total olefin yield can guarantee more than the 80wt% that the carbon back yield ratio of therein ethylene and propylene is 1.4 ~ 0.7.
MTP technology with Lurgi be representative (EP448000, DE1020050159232, WO2006136433/CN101208281A, WO192190), methyl alcohol pre-reactor (fixed bed) and MTP reactor (multistage heat-insulating fixed bed) serial operation.Methyl alcohol dewaters 250 ~ 320 ℃ of operating temperature lower parts in pre-reactor, obtain the mixed vapour of dimethyl ether, first alcohol and water, and then with/or recycle hydrocarbons be mixed into MTP main reactor (ZSM-5 zeolite molecular sieve catalyst), 450 ~ 500 ℃ down reaction to obtain propylene be main alkene, fuel gas, and gasoline etc.Lurgi MTP technology is melted salt by raw material chilling or tubulation and is controlled reaction temperature.
Oxygenatedchemicals such as methyl alcohol or dimethyl ether dehydration propylene processed is strong exothermal reaction.The MTO fluidized-bed process has good heat transfer property, and reaction temperature is easy to control.But MTO technology is the purpose product with the low-carbon alkene, if the main product propylene, needs the above alkene of the C4 of a MTO fluidized-bed reactor and C1 ~ C2 alkene are circulated to the cracking reactor (CN1962573A) in MTO downstream, to improve propene yield; Perhaps C1 ~ C2 alkene is circulated to the MTO reactor in a large number and the above alkene of C4 is circulated to cracking reactor (CN101177374A), improves propene yield.The energy consumption of above-mentioned technology and catalyst abrasion increase greatly because of a large amount of alkene circulations.Said system complexity, equipment investment and operating cost are also far above the Lurgi fixed bed reactors.
For improving propene yield, Lurgi patent (WO2006136433/CN101208281A) is circulated to multistage thin layer ZSM-5MTP main reactor with C2 and the above alkene of C4 equally, make the propylene/ethylene ratio of system be increased to 10 ~ 20, the two gross production rate reaches 73.2%(" Coal Chemical Industry ", 2005,1172, P6 ~ 7).Serious because of ZSM-5 zeolite catalyst knot carbon in its main insulation fix bed reactor, cause successive reaction to need after 400 ~ 700 hours to regenerate with the mist of air and nitrogen.Need to prove, for multistage adiabatic thin layer reaction device, regulate inlet temperature and control bed adiabatic temperature rise has certain limitation by the raw material chilling, this is because there is suitable phase mutual interference in the chilling raw material in the distribution of imports at different levels, is difficult to guarantee stable operation.
European patent DE19723363 discloses a kind of preparing propylene from methanol technology that adopts calandria type fixed bed reactor, adopts in the reactor to melt salt and remove heat indirectly, the material of equipment under the high temperature is required high, and technology is complicated, the operating cost height.
In addition, UOP discloses moving bed propylene processed (USP7,663,012, USP7,414,167) technology, and this technology is only applicable to carbon distribution speed comparatively fast but catalyst rapidly not, and moving-burden bed reactor is higher relatively to the requirement of catalyst, and the systematic comparison complexity.
Patent WO0192190A1 discloses a kind of preparing propylene from methanol technology of three reactors series connection, and reactor is axial adiabatic reactor, is provided with heat transmission equipment between every stage reactor, controls the adiabatic temperature rise of every stage reactor between 30 ~ 100 ℃.Because adopted the combination of multistage reactor, capital cost of reactor is bigger, in addition, the preheating requirement of the not integrated MTP main reactor of this combination of reactors imported raw material.
Lurgi patent DE10233975A1 discloses a kind of vertical multi-stage fixed bed reactors, and inter-stage is provided with heat exchanger and removes reaction heat, and beds is provided with pre-reactor outlet material chilling simultaneously, controls the adiabatic temperature rise of every stage reactor.It is good that this combined reactor moves thermal effect, and heat exchanger is set between the reactor has increased equipment investment, and pre-anti-material is made the inter-stage chilling and also had the adjusting interference problem.In addition, this scheme also not integrated pre-anti-outlet material to the preheating requirement of MTP main reactor import.
Chinese patent CN101876618A discloses a kind of horizontal type fixed bed reactor of producing propylene with oxygenatedchemicals (methyl alcohol/dimethyl ether), reactor is divided into the transversely arranged reaction zone of cutting apart mutually and cooling zone by porous barrier, and the cooling zone arranges the quench liquid nozzle.This reactor adopts the quench liquid cooling can control the temperature rise of each reaction zone preferably, but because there is quench liquid even distribution problem therein in quench liquid cross-current supercooling district book floor.In addition, the not integrated equally pre-anti-outlet material of this reactor arrangement is to the preheating requirement of MTP main reactor.
The utility model content
Adopt raw material chilling or tubulation to melt salt to control reaction temperature for solving existing fixed bed reactors, cause the consersion unit complexity, restive reaction moves the technical problem of heat, the utility model provides a kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell, and its technical scheme is as follows:
A kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell, comprise the main reactor that the above serial connection of one-level or one-level connects, main reactor comprises reactor shell, reactor shell is by the upper cover at top, the low head of bottom and the reactor body cylindraceous that is between upper cover and low head constitute, upper cover is provided with reacting gas inlet, low head is provided with reaction gas outlet, the upper cover below is provided with upper perforated plate, the low head top is provided with lower perforated plate, the some tubulations that are parallel to each other that vertically extend are installed between upper perforated plate and the lower perforated plate, are filled with catalyst in the tubulation;
The dividing plate that an above along continuous straight runs extends is installed between described upper perforated plate and the lower perforated plate, will be by upper perforated plate, the cavity that lower perforated plate and reactor body surround vertically is separated into two to ten not connected heat exchange shell sides, comprise the first heat exchange shell side that the cavity by between upper perforated plate and the adjacent dividing plate at the top constitutes, each following heat exchange shell side of the first heat exchange shell side is all the other heat exchange shell sides, all the other heat exchange shell sides comprise the heat exchange shell side that is made of the cavity between each adjacent dividing plate, and the heat exchange shell side that is constituted by the cavity between lower perforated plate and the adjacent dividing plate, described separator edge and reactor body are tightly connected, and described tubulation runs through dividing plate;
Be provided with the outlet of cooling medium inlet and cooling medium on the reactor body of each heat exchange shell side;
The main reactor that the above serial connection of described one-level connects refers to the reaction gas outlet of the main reactor of upper level is connected by the reacting gas inlet of pipeline with the main reactor of next stage.
As preferred version of the present utility model:
Cooling medium outlet on described all the other heat exchange shell sides is connected with reacting gas inlet with heating furnace successively by pipeline;
Cooling medium inlet on described all the other heat exchange shell sides is connected with the outlet of pre-reactor by pipeline, and pre-reactor is adiabatic reactor, comprises reactor shell, is filled with the solid catalyst aluminium oxide in reactor shell; Cooling medium inlet on the described first heat exchange shell side is connected by the outlet of pipeline with drum and hot water circulating pump system;
The outlet of described pre-reactor also is connected with the steam feeding line;
The import of described pre-reactor is connected with the material feeding tube line, and the material feeding tube line is provided with heater.
As preferred version of the present utility model:
The reaction gas outlet of described main reactor is connected with shell side medium import on first heat exchanger by pipeline;
The outlet of described pre-reactor is connected with tube side medium import on first heat exchanger, and the tube side media outlet of first heat exchanger is connected with cooling medium inlet on all the other heat exchange shell sides through pipeline.
As preferred version of the present invention:
Described steam feeding line is installed in the import of tube side medium and tube side media outlet of second heat exchanger;
Shell side media outlet on described first heat exchanger is connected with shell side medium import on second heat exchanger.
As preferred version of the present utility model:
Described material feeding tube line is installed in the import of tube side medium and tube side media outlet on the 3rd heat exchanger;
The shell side media outlet of described second heat exchanger is connected with the shell side medium import of the 3rd heat exchanger.
As preferred version of the present utility model:
The catalyst of filling in the described tubulation is the ZSM-molecular sieve;
Described cooling medium inlet and cooling medium outlet are bobbin carriage interface or ozzle, are connected with guide shell between the ozzle in each heat exchange shell side.
The method that the utility model also provides the methanol-to-olefins fixed bed production equipment of employing combinations thereof heat exchange type muitishell to produce alkene may further comprise the steps:
With the temperature lower part dehydration of methyl alcohol at 200 ~ 400 ℃, obtain the mixed system of methyl alcohol, dimethyl ether and steam;
In mixed system, feed steam then, the weight proportion that makes methyl alcohol, dimethyl ether and steam is 1:0.5 ~ 1:2, preparation obtains unstrpped gas, unstrpped gas is fed all the other heat exchange shell sides of main reactor with the shell side main shaft longitudinal cross-section superficial velocity of 5 ~ 20m/s, make it be warming up to 410 ~ 430 ℃, again by heating furnace, be warming up to 420 ~ 480 ℃ of desired reaction temperatures after, feed in the main reactor through reacting gas inlet again; The saturated boiler water of high temperature that feeds 220 ~ 280 ℃ in the first heat exchange shell side is removed heat, the high-temperature high-pressure steam of removing the formation of heat back is used for the unstrpped gas of the next working cycles of preparation; The catalyst of filling in the tubulation of described main reactor is the ZSM-5 molecular sieve;
After reaction in 2 ~ 20 seconds, obtain olefin product from reaction gas outlet, finish a working cycles.
As preferred version of the present utility model:
Described process with methyl alcohol dehydration under 200 ~ 400 ℃ of operating temperatures is finished in pre-reactor;
Cooling medium inlet on described all the other heat exchange shell sides is connected with the outlet of pre-reactor by pipeline, and pre-reactor is adiabatic reactor, comprises reactor shell, is filled with the solid catalyst aluminium oxide in reactor shell; Cooling medium inlet on the described first heat exchange shell side is connected by the outlet of pipeline with drum and hot water circulating pump system;
The outlet of described pre-reactor also is connected with the steam feeding line;
The import of described pre-reactor is connected with the material feeding tube line, and the material feeding tube line is provided with heater;
The cooling medium outlet of described all the other heat exchange shell sides is connected with reacting gas inlet with heating furnace successively by pipeline, and the unstrpped gas warp let-off heating furnace of removing the formation of heat back is heated to 410 ~ 430 ℃, feeds as unstrpped gas in the reacting gas inlet of main reactor;
The saturated boiler water of high temperature that feeds 220 ~ 280 ℃ in the first heat exchange shell side is pumped into from drum by the hot high pressure water pump, the saturated boiler water of vapoury high temperature of removing the formation of heat back forms the HTHP saturated vapor by boiler-steam dome, is used for the unstrpped gas of the next working cycles of preparation.
As preferred version of the present utility model:
The reaction gas outlet of described main reactor is connected with shell side medium import on first heat exchanger by pipeline;
The outlet of described pre-reactor is connected with tube side medium import on first heat exchanger, and the tube side media outlet of first heat exchanger is connected with cooling medium inlet on all the other heat exchange shell sides through pipeline;
With the waste heat of the olefin product in the shell body on first heat exchanger outlet material of the pre-reactor in the interior pipe on first heat exchanger is carried out preheating, its temperature is risen near the required temperature of the reacting gas inlet of main reactor;
Described steam feeding line is installed in the import of tube side medium and tube side media outlet of second heat exchanger;
Shell side media outlet on described first heat exchanger is connected with shell side medium import on second heat exchanger;
Second heat exchanger is used for the steam that feeds at mixed system is heated, and makes its temperature near the temperature of the gas of the outlet of pre-reactor;
Described material feeding tube line is installed in the import of tube side medium and tube side media outlet on the 3rd heat exchanger;
The shell side media outlet of described second heat exchanger is connected with the shell side medium import of the 3rd heat exchanger;
The 3rd heat exchanger is used for preheating or gasified methanol charging.
As preferred version of the present utility model:
The dividing plate that one to five above along continuous straight runs extends is installed between described upper perforated plate and the lower perforated plate, will vertically be separated into two to six not connected heat exchange shell sides by the cavity that upper perforated plate, lower perforated plate and reactor body surround;
Described cooling medium inlet and cooling medium outlet are the bobbin carriage interface or are ozzle, are connected with guide shell between the ozzle in each heat exchange shell side; Be communicated with bobbin carriage by the bobbin carriage interface, the saturated boiler water of high temperature or unstripped gas are passed through shell side separately by the bobbin carriage one way, perhaps the saturated boiler water of high temperature or unstripped gas are entered shell side separately by single ozzle, behind guide shell, carry out indirect countercurrent flow with high-temperature reacting gas in the tubulation;
Described unstrpped gas is 5～20m/s by the superficial velocity of shell side main shaft longitudinal cross-section.
The length of each shell side in the utility model is fixed according to tubulation internal reaction situation, the length L of tubulation equals the speed u of unstripped gas by tubulation and multiply by required time t, be L=ug * t, at the reactor inlet place, unstripped gas concentration height, reaction is violent, exothermic heat of reaction speed is fast, this moment, shell side length was short, needed in the shell side by the saturated boiler water of high temperature, removed the reaction heat in the tubulation.Than time slack, shell side length can strengthen at the tubulation internal reaction, can remove reaction heat by unstripped gas in the shell side.
The chemical equation of reacting gas in the utility model in pre-reactor is as follows:
2MEOH(methyl alcohol)=the DME(dimethyl ether)+H2O;
The chemical equation of reacting gas in the utility model in main reactor is as follows:
N MeOH=C
nH
2n+ n H
2O, n=5 ~ 9 o'clock wherein, C
nH
2nCan be ethene, propylene, C4 alkene or gasoline etc.
The utility model provides the combination heat exchange type muitishell tubulation fixed bed reactors of a kind of integrated main reaction raw material preheating and MTP exothermic heat of reaction, loading catalyst in the tubulation.But be different from common calandria type fixed bed reactor, the shell side of tubulation fixed bed reactors of the present utility model is divided into 2～10 heat exchange shell sides unequally, is preferably 2～6.Each heat exchange shell side can lead to reactor feed gas, is used for removing the exothermic heat of reaction in the tubulation on the one hand, is used for the preheating reaction feed on the other hand.Reaction feed palpus after the preheating/or by heating systems such as combustion furnaces, be warming up to the required inlet temperature of main reaction.Each heat exchange shell side also can lead to 220～280 ℃ of high temperature saturation waters (being preferably 250～260 ℃) in addition, and the interior a large amount of exothermic heat of reaction of tubulation this moment are taken away by the vaporization of saturation water.The hot generating rate of fixed bed catalyst is the product of the exothermic heat of reaction of reaction rate and the mole of unit amount, therefore the zone that must be exceedingly fast for rate of heat release, the zone that reaction rate is exceedingly fast in the tubulation, fixed bed easily forms the reaction focus in this regional tubulation, causes the reaction temperature runaway.For calandria type fixed bed reactor, react focus usually near the Reactor inlet place, apart from Reactor inlet 1/6～1/2 pipe range.Should lead to the high temperature saturation water at this interbank shell side in reaction hot spot region, in time take away a large amount of reaction heat.Shell side outside the hot spot region, exothermic heat of reaction is more slow, can lead to reaction raw materials gas and take away fixed bed reaction heat release in the tubulation, and unstrpped gas is able to preheating simultaneously, has saved the energy consumption of unstrpped gas heating furnace.
The salt that melts that is different from European patent DE19723363 complexity is removed hot system indirectly, and combination heat exchange type muitishell tubulation fixed bed reactors of the present utility model only adopt tractable high temperature saturation water or unstripped gas heat exchange, and overall structure is simplified.Adopt the high temperature saturation water can effectively take away reaction heat by-product high-pressure steam simultaneously, thereby can significantly reduce the thermoprecipitation agent in the unstripped gas, i.e. the method for the low steam proportioning of the ratio of steam, so this charging also is a kind of method for saving energy.The reaction employing ZSM-5 molecular sieve catalyst of alkene such as methyl alcohol or dimethyl ether dehydration propylene processed etc. in addition; high water vapor content causes framework of molecular sieve aluminium to run off easily under reaction temperature; cause the catalyst permanent deactivation; therefore, thisly effectively remove the activity that method reality that exothermic heat of reaction reduces steam proportioning in the charging also is conducive to guard catalyst by the combined type heat exchange.Treat that when the shell side of shell-and-tube reactor is logical preheating material gas is when removing thermal medium, can effectively utilize reaction heat to reduce the load of unstripped gas heating furnace on the one hand, on the other hand for the lower zone of exothermic heat of reaction speed, if shell side still adopts the heat exchange of high temperature saturation water, tubulation internal reaction rate of heat release may be lower than shell side and move hot speed, can cause the tubulation interior reaction temperature to continue to descend until being lower than the reaction design temperature like this, and the product of alkene such as methyl alcohol or dimethyl ether dehydration propylene processed is very responsive to reaction temperature, cross low reaction temperature and be unfavorable for generating required products such as propylene, this moment, shell side adopted the unstrpped gas heat exchange can avoid this type of problem just, also integrated simultaneously energy utilization.Wherein treat preheating material from pre-reactor, namely the pre-reactor outlet material at first by exporting the product heat exchange with the MTP main reactor, enters the shell and tube reactor shell side then, removes part MTP reaction heat.Raw material chilling between the reactor or further water cooling be means as a supplement, control the inlet temperature of every stage reactor.
Combination heat exchange type muitishell tubulation fixed bed reactors of the present utility model can be single-stage, also can be 2～4 grades, are preferably 1～2 grade.For multistage fixed bed reactor, as auxiliary temperature control method, the inter-stage material can further pass through raw material chilling or other cooling medium, as the cooling water heat exchange, guarantees the inlet temperature of every stage reactor.The utility model provides a kind of and has reduced steam proportioning in the unstripped gas, unstripped gas heating furnace load, reaches the method that prolongs catalyst life by the combination high-efficiency heat exchange.
Key problem in technology point of the present utility model is as follows:
The main reactor of alkene such as methyl alcohol or dimethyl ether dehydration propylene processed is combination heat exchange type muitishell tubulation fixed bed reactors, filling molecular sieve catalyst in the tubulation, the reactor shell side is divided into unequal a plurality of shell sides, and the shell side number can be 2～10, is preferably 2～6.Cooling medium by each shell side can be the saturated boiler water of high temperature, can also be the main reactor raw material simultaneously for the pre-reactor product also.The utility model can reduce steam proportioning in the unstripped gas, unstripped gas heating furnace load, reach the prolongation catalyst life by the combination high-efficiency heat exchange, and can guarantee that required olefin product distributes by the temperature rise of control tubulation internal reaction;
The temperature of the saturated boiler water of high temperature is 220～280 ℃, is preferably 250～260 ℃;
The main reactor unstripped gas is from the pre-reactor of preparing dimethyl ether by dewatering methanol, and process is warming up to each shell side that enters main reactor after 340～360 ℃ again with the heat exchange of main reaction product;
The saturated boiler water of high temperature should be used for the zone that the tubulation internal reaction probably forms focus, reacts focus usually near the Reactor inlet place, apart from Reactor inlet 1/6～1/2 pipe range.At the logical saturated boiler water of high temperature of the interbank shell side in this reaction hot spot region, in time take away a large amount of reaction heat;
The main reactor unstripped gas should be used for the slow zone of exothermic heat of reaction speed, reactor feed gas outside this regional tubulation enters separately, and shell side removes a part of reaction heat in the tubulation, the further intensification of unstripped gas self simultaneously, can reduce the load 10%～40% of unstripped gas heating furnace thus, be preferably 15%～30%;
Combination heat exchange type muitishell shell-and-tube reactor of the present utility model and method thereof can effectively reduce steam proportioning to 0.1～0.8 in the unstripped gas, are preferably 0.1～0.3, and more preferably 0.15～0.25.
Cooling medium (the saturated boiler water of high temperature or unstripped gas) can pass through shell side separately by a comb packing list journey, also can enter shell side separately by single ozzle, guide shell is set, with the indirect countercurrent flow of high-temperature reacting gas in the tubulation in shell side.
Be further elaborated below by the utility model of embodiment, these schemes only are to further specify rather than the scope of limit value claims.
Description of drawings
Fig. 1 is olefin process schematic flow sheets such as the utility model methyl alcohol or dimethyl ether dehydration propylene processed;
Fig. 2 is that alkene, combination heat exchange type muitishell shell-and-tube reactor such as methyl alcohol or dimethyl ether dehydration propylene processed arranged schematic diagram among Fig. 1, and wherein cooling medium passes through each shell side by the bobbin carriage one way;
Fig. 3 is that alkene, combination heat exchange type muitishell shell-and-tube reactor such as methyl alcohol or dimethyl ether dehydration propylene processed arranged schematic diagram among Fig. 1, and wherein cooling medium enters each shell side by ozzle;
Fig. 4 is the operating curve of combination heat exchange type muitishell tubulation fixed bed reactors of the present utility model;
Fig. 5 is the cutaway view of the main reactor among Fig. 1.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the utility model.Should be understood that embodiment only is used for explanation the utility model and is not used in the scope of the present utility model that limits.Should be understood that in addition those skilled in the art can make various changes or modifications the utility model after the content of having read the utility model instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
A kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell, as shown in Figure 5, comprise the main reactor 11 that the above serial connection of one-level or one-level connects, main reactor 11 comprises reactor shell 19, reactor shell 19 is by the upper cover 20 at top, the low head 21 of bottom and the reactor body 22 cylindraceous that is between upper cover 20 and low head 21 constitute, upper cover 20 is provided with reacting gas inlet 23, low head 21 is provided with reaction gas outlet 24, upper cover 20 belows are provided with upper perforated plate 25, low head 21 tops are provided with lower perforated plate 26, the some tubulations that are parallel to each other 12 that vertically extend are installed between upper perforated plate 25 and the lower perforated plate 26, are filled with catalyst in the tubulation 12;
The dividing plate 27 that an above along continuous straight runs extends is installed between described upper perforated plate 25 and the lower perforated plate 26, will be by upper perforated plate 25, the reactor shell side that lower perforated plate 26 and reactor body 22 surround vertically is separated into two to ten not connected heat exchange shell sides, wherein constitute the first heat exchange shell side 13 by upper perforated plate 25 and the adjacent cavity between the dividing plate 27 at top thereof, by lower perforated plate 26 and the adjacent cavity between the dividing plate 27 of bottom thereof, and the cavity between each adjacent dividing plate 27 constitutes all the other heat exchange shell sides 28, all the other heat exchange shell sides 28 comprise the second heat exchange shell side 14, N heat exchange shell side 15, N=2～10, preferred N=2～6, described dividing plate 27 edges and reactor body 22 are tightly connected, and described tubulation 12 runs through dividing plate 27;
Be provided with cooling medium inlet 29 and cooling medium outlet 30 on the reactor body 22 of each heat exchange shell side 28;
The main reactor 11 that the above serial connection of described one-level connects refers to the reaction gas outlet 24 of the main reactor 11 of upper level is connected by the reacting gas inlet 23 of pipeline with the main reactor 11 of next stage.
As shown in Figure 1, the outlet 30 of the cooling medium of described all the other heat exchange shell sides 28 is connected with reacting gas inlet 23 with heating furnace 7 successively by pipeline;
Cooling medium inlet 29 on described all the other heat exchange shell sides 28 is connected by the outlet of pipeline with pre-reactor 4, and pre-reactor 4 is adiabatic reactor, comprises reactor shell, is filled with the solid catalyst aluminium oxide in reactor shell; Cooling medium inlet 29 on the described first heat exchange shell side 13 is connected by the outlet of pipeline with drum and hot water circulating pump system 34;
The outlet of described pre-reactor 4 also is connected with steam feeding line 10;
The import of described pre-reactor 4 is connected with material feeding tube line 1, and material feeding tube line 1 is provided with heater 3.
The reaction gas outlet 24 of described main reactor 11 is connected with shell side medium import on first heat exchanger 5 by pipeline;
The outlet of described pre-reactor 4 is connected with the tube side medium import of first heat exchanger 5, and the tube side media outlet of first heat exchanger 5 is connected with cooling medium inlet 29 on all the other heat exchange shell sides 28 through pipeline.
Described steam feeding line 10 is installed in the import of tube side medium and tube side media outlet of second heat exchanger 9;
Shell side media outlet on described first heat exchanger 5 is connected with shell side medium import on second heat exchanger 9.
Described material feeding tube line 1 is installed in the import of tube side medium and tube side media outlet on the 3rd heat exchanger 2;
The shell side media outlet of described second heat exchanger 9 is connected with the shell side medium import of the 3rd heat exchanger 2.
The catalyst of filling in the described tubulation 12 is the ZSM-5 molecular sieve;
Described cooling medium inlet 29 and cooling medium outlet 30 are bobbin carriage interface or ozzle, are connected with guide shell between the ozzle in each heat exchange shell side.
As shown in Figure 1, the method with above-mentioned a kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell is produced alkene may further comprise the steps:
With the temperature lower part dehydration of methyl alcohol at 200 ~ 400 ℃, obtain the mixed system of methyl alcohol, dimethyl ether and steam;
In mixed system, feed steam then, the weight proportion that makes methyl alcohol, dimethyl ether and steam is 1:0.5 ~ 1:2, preparation obtains unstrpped gas, unstrpped gas is after main reactor shell side and heating furnace 7 are warmed up to 420 ~ 480 ℃, as unstripped gas after the preheating 17, feeding in the main reactor 11 through described reacting gas inlet 23. unstripped gas 17 is 5 ~ 20m/s by the superficial velocity of shell side main shaft longitudinal cross-section after the preheating.The saturated boiler water 32 of high temperature that feeds 220 ~ 280 ℃ in the first heat exchange shell side 13 is removed heat, and the high-temperature high-pressure steam 33 of removing the formation of heat back is used for the unstrpped gas of the next working cycles of preparation or is used for other technology.In all the other heat exchange shell sides 28, feed unstrpped gas 16 and remove heat, be 410 ~ 430 ℃ unstrpped gas 31 and steam proportioning with removing temperature that heat back forms, make the weight proportion of methyl alcohol, dimethyl ether and steam reach 1:0.5 ~ 1:2, again after heating furnace 7 is warmed up to 420 ~ 480 ℃, as unstripped gas 17 after the preheating of next working cycles, feed again the main reactor 11 from reacting gas inlet 23, the catalyst of filling in the tubulation 12 of described main reactor 11 is the ZSM-5 molecular sieve;
After reaction in 2 ~ 20 seconds, obtain olefin product 18 from reaction gas outlet 24, finish a working cycles.
Described process with methyl alcohol dehydration under 200 ~ 400 ℃ of operating temperatures is finished in pre-reactor 4;
Cooling medium inlet 29 on described all the other heat exchange shell sides 28 is connected by the outlet of pipeline with pre-reactor 4, and pre-reactor 4 is adiabatic reactor, comprises reactor shell, is filled with the solid catalyst aluminium oxide in reactor shell; Cooling medium inlet 29 on the described first heat exchange shell side 13 is connected by the outlet of pipeline with drum and hot water circulating pump system 34;
The outlet of described pre-reactor 4 also is connected with steam feeding line 10;
The import of described pre-reactor 4 is connected with material feeding tube line 1, and material feeding tube line 1 is provided with heater 3;
The cooling medium outlet 30 of described all the other heat exchange shell sides 28 is connected with reacting gas inlet 23 with heating furnace 7 successively by pipeline, unstrpped gas 31 warp let-off heating furnaces 7 of removing the formation of heat back are heated to 420 ~ 480 ℃, feed in the reacting gas inlet 23 of main reactors 11 as unstripped gas after the preheating of next working cycles 17;
The saturated boiler water 32 of 220 ~ 280 ℃ high temperature that feeds in the first heat exchange shell side 13 is pumped into from drum by the hot high pressure water pump, the saturated boiler water 33 of vapoury high temperature of removing the formation of heat back forms HTHP saturated vapor 35 by boiler-steam dome, for unstripped gas 17 or other technology after the preheating of the next working cycles of preparation.
The reaction gas outlet 24 of described main reactor 11 is connected with shell side medium import on first heat exchanger 5 by pipeline;
The outlet of described pre-reactor 4 is connected with the tube side medium import of first heat exchanger 5, and the tube side media outlet of first heat exchanger 5 is connected with cooling medium inlet 29 on all the other heat exchange shell sides 28 through pipeline;
With the waste heat of the olefin product in the shell side on first heat exchanger 5 outlet material of the pre-reactor 4 in the tube side on first heat exchanger 5 is carried out preheating, its temperature is risen near the required temperature of the reacting gas inlet 23 of main reactor 11;
Described steam feeding line 10 is installed in the import of tube side medium and tube side media outlet of second heat exchanger 9;
Shell side media outlet on described first heat exchanger 5 is connected with shell side medium import on second heat exchanger 9;
Second heat exchanger 9 is used for the steam that feeds at mixed system is heated, and makes its temperature near the temperature of the gas of the outlet of pre-reactor 4;
Described material feeding tube line 1 is installed in the import of tube side medium and tube side media outlet on the 3rd heat exchanger 2;
The shell side media outlet of described second heat exchanger 9 is connected with the shell side medium import of the 3rd heat exchanger 2;
The 3rd heat exchanger 2 is used for preheating or gasified methanol charging.
Described cooling medium inlet 29 and cooling medium outlet 30 are the bobbin carriage interface or are ozzle, are connected with guide shell between the ozzle in each heat exchange shell side; As shown in Figure 2, be communicated with bobbin carriage by the bobbin carriage interface, the saturated boiler water 32 of high temperature or unstripped gas 16 are passed through shell side separately by the bobbin carriage one way, perhaps as shown in Figure 3, the saturated boiler water 32 of high temperature or unstripped gas 16 are entered shell side separately by single ozzle, behind guide shell, carry out indirect countercurrent flow with high-temperature reacting gas in the tubulation;
Fig. 4 is the operating curve of combination heat exchange type muitishell tubulation fixed bed reactors of the present utility model, and wherein Tin is reactor inlet temperatures, also is catalytic reaction required " igniting " temperature.Tout1 is the reactor outlet temperature, also is the ceiling temperature that catalytic reaction allows.Tout2 is fixed bed reactors adiabatic operation curve in the tubulation, and this moment, Tout2 surpassed the upper limit that catalytic reaction allows.For olefine reactions such as methyl alcohol or dimethyl ether dehydration propylene processed, overtemperature not only can aggravate catalyst coking and inactivation, and can cause that undesirable methane content significantly increases in the product.Therefore combination high-efficiency heat-exchange method of the present utility model not only can reduce steam proportioning in the unstripped gas, unstripped gas heating furnace load, reach the prolongation catalyst life, and can guarantee that required olefin product distributes by the temperature rise of control tubulation internal reaction.
In brief, Fig. 1 is olefin process schematic flow sheets such as methyl alcohol or dimethyl ether dehydration propylene processed.As shown in Figure 1, a kind of calandria type fixed bed reactor and technology thereof for preparing propylene from methanol comprise following capital equipment: the methyl alcohol partial dehydration generates the pre-reactor 4 of dimethyl ether (DME); The main reactor 6 of alkene such as methyl alcohol or dimethyl ether dehydration propylene processed; Main reactor unstripped gas heater (as heating furnace) 7; 3 heat exchangers of main reactor outlet material, wherein first heat exchanger 5 is used for preheating pre-reactor outlet material, its temperature is risen near the required temperature of main reactor import, second heat exchanger 9 is used for the required supplementing water steam of vaporization main reactor, and the 3rd heat exchanger 2 is used for preheating or gasified methanol charging; Heat exchanger 5 is used for heating methanol steam to the required feeding temperature of pre-reactor; The saturated boiler water 32 of high temperature; The saturated boiler water 33 of vapoury high temperature; Drum and hot water circulating pump system 34; HTHP saturated vapor 35.Methanol feedstock enters this reaction system by pipeline 1, and the required supplementing water steam of main reactor then enters this reaction system by pipeline 10.
As Fig. 1, methyl alcohol or dimethyl ether come to enter insulation fix bed pre-reactor 4 after heating with the heat exchange of main reactor exit gas and heater 3, and the operating temperature of pre-reactor is 200～400 ℃, is preferably 240～360 ℃.The operating temperature of main reactor 6 is 420～500 ℃, is preferably 460～480 ℃.High temperature main reactor exit gas is used for further heating pre-reactor outlet raw material, makes it be warming up to 340～360 ℃, enters shell and tube main reactor shell side again as cooling medium.Shell and tube main reactor of the present utility model is muitishell combination heat exchange type tubulation fixed bed reactors, and the reactor shell side also can feed the saturated boiler water of high temperature as cooling medium except the unstripped gas that feeds from pre-reactor.The temperature of the saturated boiler water of high temperature is 220～280 ℃, is preferably 250～260 ℃.Cooling medium enters the mode of shell side and sees Fig. 2.
Fig. 2 is combination heat exchange type muitishell tubulation fixed bed reactors schematic diagram of the present utility model, comprises single-stage or multistage reactor 11; The tubulation 12 of loading catalyst; The one the second, and N level shell side, the i.e. first heat exchange shell side 13, the second heat exchange shell side 14, N heat exchange shell side 15; Heat transferring medium (the saturated boiler water 32 of high temperature or unstripped gas 16); Unstripped gas 17 after the preheating; And product is olefin product 18.
As Fig. 2, from the unstripped gas of pre-reactor 4 by a comb packing list journey by each shell side of shell-and-tube reactor, or enter each shell side as Fig. 3 unstripped gas by ozzle, the layout guide shell makes cooling medium and the indirect countercurrent flow of tubulation internal reaction material in the shell side.
Claims (6)
1. methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell, comprise the main reactor (11) that the above serial connection of one-level or one-level connects, main reactor (11) comprises reactor shell (19), reactor shell (19) is by the upper cover (20) at top, the low head (21) of bottom and be positioned at upper cover (20) and low head (21) between be reactor body cylindraceous (22) formation, upper cover (20) is provided with reacting gas inlet (23), low head (21) is provided with reaction gas outlet (24), upper cover (20) below is provided with upper perforated plate (25), low head (21) top is provided with lower perforated plate (26), the some tubulations that are parallel to each other (12) that vertically extend are installed between upper perforated plate (25) and the lower perforated plate (26), and tubulation is filled with catalyst in (12);
It is characterized in that:
The dividing plate (27) that an above along continuous straight runs extends is installed between described upper perforated plate (25) and the lower perforated plate (26), will be by upper perforated plate (25), the cavity that lower perforated plate (26) and reactor body (22) surround vertically is separated into two to ten not connected heat exchange shell sides, comprise the first heat exchange shell side (13) that the cavity by between upper perforated plate (25) and the adjacent dividing plate (27) that is positioned at the top constitutes, each following heat exchange shell side of the first heat exchange shell side (13) is all the other heat exchange shell sides (28), all the other heat exchange shell sides (28) comprise the heat exchange shell side that is made of the cavity between each adjacent dividing plate (27), and the heat exchange shell side that is constituted by the cavity between lower perforated plate (26) and the adjacent dividing plate (27), described dividing plate (27) edge and reactor body (22) are tightly connected, and described tubulation (12) runs through dividing plate (27);
Be provided with cooling medium inlet (29) and cooling medium outlet (30) on the reactor body of each heat exchange shell side (22);
The main reactor (11) that the above serial connection of described one-level connects refers to the reaction gas outlet (24) of the main reactor (11) of upper level is connected by the reacting gas inlet (23) of pipeline with the main reactor (11) of next stage.
2. a kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell according to claim 1 is characterized in that:
Cooling medium outlet (30) on described all the other heat exchange shell sides (28) is connected with reacting gas inlet (23) with heating furnace (7) successively by pipeline;
Cooling medium inlet (29) on described all the other heat exchange shell sides (28) is connected by the outlet of pipeline with pre-reactor (4), and pre-reactor (4) is adiabatic reactor, comprises reactor shell, is filled with the solid catalyst aluminium oxide in reactor shell; Cooling medium inlet (29) on the described first heat exchange shell side (13) is connected by the outlet of pipeline with drum and hot water circulating pump system (34);
The outlet of described pre-reactor (4) also is connected with steam feeding line (10);
The import of described pre-reactor (4) is connected with material feeding tube line (1), and material feeding tube line (1) is provided with heater (3).
3. a kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell according to claim 1 is characterized in that:
The reaction gas outlet (24) of described main reactor (11) is connected with shell side medium import on first heat exchanger (5) by pipeline;
The outlet of described pre-reactor (4) is connected with tube side medium import on first heat exchanger (5), and the tube side media outlet of first heat exchanger (5) is connected with cooling medium inlet (29) on all the other heat exchange shell sides (28) through pipeline.
4. a kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell according to claim 3 is characterized in that:
Described steam feeding line (10) is installed in the import of tube side medium and tube side media outlet of second heat exchanger (9);
Shell side media outlet on described first heat exchanger (5) is connected with shell side medium import on second heat exchanger (9).
5. a kind of methanol-to-olefins fixed bed production equipment that makes up the heat exchange type muitishell according to claim 4 is characterized in that:
Described material feeding tube line (1) is installed in the import of tube side medium and tube side media outlet on the 3rd heat exchanger (2);
The shell side media outlet of described second heat exchanger (9) is connected with the shell side medium import of the 3rd heat exchanger (2).
6. according to claim 1,2,3,4 or 5 described a kind of methanol-to-olefins fixed bed production equipment that make up the heat exchange type muitishell, it is characterized in that:
The catalyst of filling in the described tubulation (12) is the ZSM-5 molecular sieve;
Described cooling medium inlet (29) and cooling medium outlet (30) are bobbin carriage interface or ozzle, are connected with guide shell between the ozzle in each heat exchange shell side.
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| CN2012207434188U CN203170305U (en) | 2012-12-29 | 2012-12-29 | Combined-heat-exchange multi-shell-side fixed bed production equipment for preparing olefin from methanol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908929A (en) * | 2012-12-29 | 2014-07-09 | 新煤化工设计院（上海）有限公司 | Combined heat exchange type multi-shell side methanol-to-olefin fixed bed production equipment and production method thereof |
| CN106010626A (en) * | 2016-07-08 | 2016-10-12 | 成都赛普瑞兴科技有限公司 | Process of preparing stable light hydrocarbon through methanol conversion in isothermal method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908929A (en) * | 2012-12-29 | 2014-07-09 | 新煤化工设计院（上海）有限公司 | Combined heat exchange type multi-shell side methanol-to-olefin fixed bed production equipment and production method thereof |
| CN103908929B (en) * | 2012-12-29 | 2016-12-28 | 新煤化工设计院（上海）有限公司 | A kind of methanol-to-olefins fixed bed production equipment combining heat exchange type muitishell and production method thereof |
| CN106010626A (en) * | 2016-07-08 | 2016-10-12 | 成都赛普瑞兴科技有限公司 | Process of preparing stable light hydrocarbon through methanol conversion in isothermal method |
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