CN110054539A - A kind of preparing propylene from methanol device and method - Google Patents
A kind of preparing propylene from methanol device and method Download PDFInfo
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- CN110054539A CN110054539A CN201910387539.XA CN201910387539A CN110054539A CN 110054539 A CN110054539 A CN 110054539A CN 201910387539 A CN201910387539 A CN 201910387539A CN 110054539 A CN110054539 A CN 110054539A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a kind of preparing propylene from methanol device, described device includes first reactor, the first conveying pipeline, the second conveying pipeline, third conveying pipeline, cooling unit, dimethyl ether knockout tower, heating furnace, second reactor, separative unit, four rectifying column of carbon, recycle hydrocarbons pipeline and steam pipe line；The invention also discloses corresponding preparing propylene from methanol methods；The present invention, which separates iso-butane from recycle hydrocarbons and first reactor is carried out obtained first product stream of preparing dimethyl ether from methanol reaction, is divided into three strands, the dispersion charging arranged in pairs or groups by different temperatures, help to reduce reactor temperature runaway phenomenon, simultaneously by adjusting the gas liquid ratio by side entry feed, facilitate the efficiently controlling temperature of reactor.
Description
Technical field
The present invention relates to preparing propylene from methanol fields, more particularly to a kind of methanol system third that can effectively improve propene yield
Alkene device and method.
Background technique
Propylene is the most important basic organic for being only second to ethylene.With the expansion year by year of its derivative application field
Exhibition, demand is growing day by day, but increasingly plaque is weary for petroleum resources, and there is an urgent need to develop the propylene preparation process of non-petroleum base.Currently,
Entered large-scale production using coal/natural gas as raw material methanol, preparing light olefins from methanol (MTO/MTP) have raw material extensively,
The advantages that at low cost, the national conditions for being suitble to China rich in coal and poor in oil.
Preparing propylene from methanol (MTP) technique is that under the effect of the catalyst, chemical reaction life occurs for dimethyl ether/methanol mixture
At gaseous mixture include hydrocarbon mixture and other compounds, such as CO, CO2, H2O, the gaseous mixture is through Waste Heat Recovery System
Recycle heat after, need to further decrease temperature, condense and separate.Vapor and liquid hydrocarbon and unreacted methanol are condensed and divide
From final reacting product can be divided into tail gas, liquid hydrocarbon and process water.
In October, 2010,500,000 tons/year of coal-based methanol systems third that Shenhua Ningxia Coal Industry Group is introduced from German Lurgi company
Alkene (MTP) project puts into industrial production.So far, which ran more than 6 years.As most of industrialized for the first time large
Chemicals production technology is the same, and Lurgi MTP technique needs to improve it there is also many places while highly selective production propylene
Place.In MTP device operational process, how to maintain productivity of propylene to stablize is always the bottleneck for perplexing device even running.Due to anti-
It answers exothermic heat of reaction in device obvious, is easy to cause bed that temperature runaway phenomenon occurs.
In addition, catalyst will undergo activity inducement phase, active rising stage, the active stage of stable development and work in MTP reaction process
Four different phases such as property decline phase.When catalyst is in activity inducement phase and active rising stage, due to acidity of catalyst compared with
By force, there is the generation of the side reactions such as more hydrogen migration in reaction, cause target product propene yield in product lower.In practical operation
In, for the total recovery for improving target product propylene, the hydro carbons (recycle hydrocarbons) after product need to be separated to ethylene and propylene is recycled back to MTP
Reactor continues to convert, so that the reaction in reactor is increasingly complex, in addition bed temperature runaway, it is easier to lead to urging in reactor
Agent coking and deactivation, influences product yield.
On the other hand, very high as iso-butane in C4 hydrocarbon a part of in recycle hydrocarbons and normal butane content, up to
55wt%.Mix the components such as the main isobutene of C4,1- butylene, 2- butylene, iso-butane, normal butane.In Lurgi MTP technique,
C4 hydrocarbon returns to MTP reactor.Since the presence of high-content alkane will increase C4 circulating consumption and heater loads；On the other hand make
To sell outside LPG mixed material, the waste of alkene is also resulted in.In fact, iso-butane and normal butane content are not involved in circulation C4 hydrocarbon
Reaction, therefore wherein too high levels, seriously affect the yield of propylene.
Summary of the invention
The purpose of the present invention is to provide one kind by preparing propylene from methanol device and method, with the steady efficient fortune of realization device
Row.
One aspect to achieve the above object, the invention adopts the following technical scheme:
A kind of preparing propylene from methanol device, described device include:
First reactor, for carrying out preparing dimethyl ether from methanol reaction, to obtain the first product stream；
It is respectively used to the first conveying pipeline, the second conveying pipeline and third conveying pipeline of the first product stream of transport portion；
Cooling unit, for being cooled down to the first product stream from first conveying pipeline；
Dimethyl ether knockout tower, for being separated to the first product stream from the cooling unit, in dimethyl ether point
From the rich dimethyl ether gaseous stream that top of tower is isolated, liquid phase stream is obtained in bottom；
Second reactor, for carrying out the reaction of the first product stream propylene, to obtain the second product stream；Second reaction
Multiple catalyst beds are equipped in device along longitudinal direction, and further respectively have between adjacent catalyst bed second reactor into
Expect side line, the second reactor feeds the side line top with the third conveying pipeline and the dimethyl ether knockout tower respectively
Connected with bottom, for by the first product stream from the third conveying pipeline and from the dimethyl ether knockout tower extremely
Small part gaseous stream and at least partly liquid phase stream are sent into the second reactor；
Separative unit, for being separated to second product stream, rectifying, to isolate C4 hydrocarbon stream, be followed as first
C2 the and C5-C6 hydrocarbon stream and C3 hydrocarbon stream of cyclic hydrocarbon stream (for propylene and propane)；
Four rectifying column of carbon, for the C4 hydrocarbon stream carry out rectifying separation, so as to tower top isolate C4 alkane to
Tower bottom obtains the C4 rich olefins as second circulation hydrocarbon stream；
Recycle hydrocarbons pipeline, for receiving at least partly described first circulation hydrocarbon stream and at least partly described second circulation hydrocarbon
Stream, using a part of the top feed as the second reactor；
Steam pipe line, for conveying water vapour, using a part of the top feed as the second reactor；
Heating furnace, for reacting wait enter second from second conveying pipeline, recycle hydrocarbons pipeline and steam pipe line
Mixed material at the top of device is heated, using the top feed as second reactor.
The apparatus according to the invention, it is preferable that described device further includes waste heat recovery unit, for making wait enter described point
From the second product stream of unit respectively with the desalted water for producing the vapor and wait be sent into the first reactor top
The methanol charging heat exchange cooling in portion；The steam pipe line is for conveying the desalted water successively through the waste heat recovery unit and institute
State the heating obtained vapor of stove heating.
The apparatus according to the invention, it is preferable that multiple catalyst beds are equipped in the first reactor along longitudinal direction, and
First reactor charging side line is additionally provided between adjacent catalyst bed, the first reactor charging side line is used for first
Alcohol feeds to the first reactor；Preferably, layer 2-3 catalyst bed is equipped in the first reactor.
The apparatus according to the invention, it is preferable that the cooling unit includes the first cooler and the second cooler, and described the
One cooler is used to that the first product stream conveyed via first conveying pipeline to be made to follow with what is conveyed via the recycle hydrocarbons pipeline
The heat exchange cooling of cyclic hydrocarbon stream；Second cooler is used to make to flow into one via the first product of first cooler heat exchange cooling
Step feeds heat exchange cooling with the methanol wait be sent into the waste heat recovery unit.
The apparatus according to the invention, it is preferable that 4-8 layers, such as 5 or 6 layers of catalyst bed are equipped in the second reactor
Layer；It is further preferred that any Intermediate Catalyst bed of the second reactor and below between adjacent catalyst bed
Spacing is 1.1-1.2 times of the spacing between its top adjacent catalyst bed layer, namely from top to bottom, thus the first of the top
Catalyst bed is to the most end catalyst bed of bottom, and spacing becomes larger between adjacent catalyst bed.
Another aspect for achieving the above object, the present invention adopts the following technical scheme:
A kind of method of preparing propylene from methanol carries out methanol to propylene reaction using above-mentioned device；Wherein, first is come from
The accounting 8-15wt% of reactor, such as the first product stream of 10wt% or 12wt% enter the second conveying pipeline, accounting 55-
65wt%, such as the first product stream of 58wt%, 60wt% or 62wt% enter third conveying pipeline and remaining first product
Stream enters the first conveying pipeline.
Method in accordance with the invention it is preferred that the C4 hydrocarbon stream is all sent into four rectifying column of carbon, deviate from most of isobutyl
Alkane obtains C4 fulvene the hydrocarbon component, and iso-butane content is not more than 15wt% in the C4 fulvene the hydrocarbon component (second circulation hydrocarbon stream), excellent
Choosing is not more than 5wt%, such as 2wt% or 4wt%.
Method in accordance with the invention it is preferred that the liquid phase stream from the dimethyl ether knockout tower is entering described second
Temperature is controlled before reactor feed side line to 65 DEG C hereinafter, preferably controlling temperature to 45-60 DEG C, such as 50 or 55 DEG C.
Method in accordance with the invention it is preferred that the methanol charging of the first reactor be divided into the charging of first strand of methanol and
Second burst of methanol charging；Wherein, first strand of methanol charging accounts for 50wt%~70wt% of the methanol charging, such as
55wt%, 60wt% or 65wt% are sent after being preheated to 260 DEG C~300 DEG C, such as 270,280 or 290 DEG C to first reaction
The first catalyst bed counted from the top down in device；Second strand of methanol charging is not preheated, from the first reactor side
Face send respectively to remaining catalyst bed (obtain the first product stream temperature preferably can for 340~380 DEG C, such as 350,360 or
370℃)；The tower top feeding temperature of the second reactor is 430~470 DEG C, such as 450 or 460.
In order to guarantee the efficient progress of catalytic cracking reaction, catalyst preferably has stronger acids in the second reactor
The HZSM-5 molecular sieve catalyst of property, such as HZSM-5 molecular sieve catalyst disclosed in CN104556134B；Specifically, described
Catalyst is prepared by the following method in second reactor, comprising:
(1) by organic ammonium salt waterglass and water be in molar ratio organic ammonium salt: SiO2:H2O=0.05~0.5:1:10~
40 are mixed into mixed liquor A；
It (2) is in molar ratio Al by aluminium salt, the concentrated sulfuric acid and water2O3:H2SO4:H2O=1:25~450:500~5700 is mixed
At mixed liquid B；
(3) mixed liquid B is added drop-wise in mixed liquor A, adjusts pH=9.5~12, be uniformly mixed: in 80~100 DEG C of conditions
Under evaporate 30~90% water, be added fatty amine, be uniformly mixed, be made gel mixture；
(4) gel mixture is added in synthesis reactor, sealing first carries out aging at 80~110 DEG C, then 170~190
Crystallization is carried out at DEG C；
(5) terminate crystallization, isolated solid is roasted at 520~560 DEG C, uses inorganic ammonium salt solution later
Ion exchange is carried out, filtered filter cake is at 500~550 DEG C, for example 540 DEG C roast 2.5~4 hours, such as 3 hours, obtain
To HZSM-5 molecular sieve catalyst.
Compared with prior art, first reactor is carried out obtained first product of preparing dimethyl ether from methanol reaction by the present invention
Stream is divided into three strands, the gas-liquid two-phase of cold conditions is further separated into after first burst of logistics is cooling in dimethyl ether knockout tower, through side line
Into each catalyst layer of second reactor；Second burst of logistics enters the first catalyst bed of second reactor from top；Third stock
Logistics is directly through the side entry feed of second reactor；Since temperature covers high, normal, basic three levels after processing for three bursts of logistics, lead to
The dispersion charging for crossing the collocation of second reactor side different temperatures, helps to reduce reactor temperature runaway phenomenon, while passing through adjusting
By the gas liquid ratio of side entry feed, facilitate the efficiently controlling temperature and stability of reactor；
In addition, being mainly that iso-butane is isolated by C4 alkane therein by newly-installed C4 knockout tower in the present invention
Come, to improve as the olefin(e) centent in the C4 hydrocarbon of recycle hydrocarbons, to improve when catalyst activity is high, C4 alkene is opposite to be fed
Amount reduces propene yield fluctuation；
In addition, catalyst bed interlamellar spacing from top to bottom incrementally increases in second reactor in the present invention, the second reaction is complied with
The design of material from top to bottom multilayer secondary response in device especially cooperates and above-mentioned first product stream is divided into setting for three strands of materials
Meter, is conducive to device and runs smoothly, propene yield is higher.
Detailed description of the invention
Fig. 1 is the schematic diagram of one embodiment of the present invention.
Specific embodiment
Below in conjunction with attached drawing, the present invention is described in detail, but it should be recognized that the present invention is not limited to this.
As shown in Figure 1, catalyst for producing propylene with methanol evaluating apparatus of the invention includes first reactor 101, the first conveying
Pipe 5, the second conveying pipeline 4 and third conveying pipeline 3, cooling unit, dimethyl ether knockout tower 107, heating furnace 110, second reactor
102, separative unit 104, four rectifying column 105 of carbon, recycle hydrocarbons pipeline 6 and steam pipe line 10.
Wherein, the first reactor 101 is used to carry out preparing dimethyl ether from methanol reaction by raw material of methanol, to obtain first
Product stream.Those skilled in the art are readily apparent that first product stream generally includes dimethyl ether, water and unreacted methanol.
In one embodiment, along longitudinal direction equipped with 2 first reactor catalyst beds 1 in the first reactor 101, and
First reactor charging side line 11 is additionally provided between adjacent first reactor catalyst bed 1, so that methanol charging can be certainly
Enter the first reactor 101 through first reactor charging side line 11 while 101 top feed of first reactor and carries out first
Alcohol reaction of preparing dimethyl ether.Since preparing dimethyl ether from methanol reaction is exothermic reaction, enter through first reactor charging side line 11
The lower methanol charging of the temperature of the first reactor 101 can help to adjust the temperature in the first reactor 101, prevent
Only temperature runaway.Preferably, layer 2-3 first reactor catalyst bed 1 is equipped in the first reactor 101.
The first product stream for leaving the first reactor 101 is divided into three strands, defeated by the first conveying pipeline 5, second respectively
Expects pipe 4 and third conveying pipeline 3 convey.
The cooling unit (not marking in figure) is for cooling down the first product stream from first conveying pipeline 5
Cooling.In one embodiment, the cooling unit includes the first cooler 108 and the second cooler 109, and described first is cooling
Device 108 is used to that the first product stream conveyed via first conveying pipeline 5 and circulation hydrocarbon stream heat exchange to be made to cool down；Described second is cooling
Device 109 is used to make further to feed heat exchange cooling with methanol via the first product stream of first cooler 108 heat exchange cooling,
The methanol charging is preheated simultaneously, helps to cause the anti-of preparing dimethyl ether from methanol, methanol charging finally will be described as being sent to
The methanol charging at 101 top of first reactor.
The dimethyl ether knockout tower 107 is used to carry out gas-liquid separation to the first product stream from the cooling unit, with
The gaseous stream that the rich dimethyl ether of cold conditions is obtained at the top of dimethyl ether knockout tower 107, bottom obtain cold conditions predominantly water and
The liquid phase stream of methanol, the gas isolated can be from the Base top contacts of the dimethyl ether knockout tower, and the liquid isolated can be with
It is drawn from the bottom of the dimethyl ether knockout tower.
The top feed that the heating furnace 110 is used to treat into 102 top of second reactor is heated, the top
Charging includes the first product stream from second conveying pipeline 4 and the material from recycle hydrocarbons pipeline 6 and steam pipe line 10,
In order to which the material entered at the top of the second reactor 102 can be carried out smoothly at the top of the second reactor 102
Reaction.
The second reactor 102 is for carrying out the reaction of the first product stream propylene, to obtain the second product stream；Described
Multiple second reactor catalyst beds 9 are equipped in two reactors 102 along longitudinal direction, and in adjacent second reactor catalyst
Further respectively have second reactor charging side line 7 between bed 9, second reactor charging side line 7 by pipeline respectively with
The connection of the top and bottom of the third conveying pipeline 3 and the dimethyl ether knockout tower 107, it is defeated for the third will to be come from
First product stream of expects pipe 3 and at least partly gaseous stream from the dimethyl ether knockout tower 107 and at least partly liquid phase
The second reactor 102 is sent into logistics.
It will be appreciated by those skilled in the art that since 102 top feed temperature of second reactor is higher, it can be in the first catalyst
Reaction is gone on smoothly under the action of bed, simultaneously because the reaction carried out in the second reactor 102 is similarly exothermic reaction,
The the first not preheated product stream for entering the second reactor 102 through second reactor charging side line 7 not only can be with
Play the role of dispersion charging, while exothermic heat of reaction can also be utilized, facilitates energy conservation；Finally, being separated from the dimethyl ether
The lower gaseous stream of the temperature of tower 107 and liquid phase stream then can prevent temperature runaway with the temperature in Effective Regulation reactor.It is preferred that
Ground is equipped with 3-8 layers, such as 5 or 6 layers of second reactor catalyst bed 9 in the second reactor 102.
The separative unit 104 for second product stream is separated, rectifying, to isolate C4 hydrocarbon stream, first
Recycle hydrocarbon stream and target product propylene；Using the difference of the boiling point of each component in mixture to be separated to mixture
To be known in the art, for example, the separative unit 104 may include multiple rectifying columns, may be implemented by cooperation to mixing
The gradually separation of object, to be known in the art, which is not described herein again.
Four rectifying column 105 of carbon is used to carry out rectifying separation to the C4 hydrocarbon stream, to obtain C4 alkane, tower in tower top
Bottom obtains the C4 rich olefins as second circulation hydrocarbon stream；Iso-butane and normal butane content are very high in C4 hydrocarbon stream, wherein iso-butane
Rectificating method can be used to isolate from tower top, to increase the relative amount of C4 alkene in second circulation hydrocarbon stream, help to increase
Add the yield of target product propylene.
The recycle hydrocarbons pipeline 6 is for receiving at least partly described first circulation hydrocarbon stream and at least partly described second circulation
Hydrocarbon stream, using a part as the top feed.The steam pipe line 10 for conveying water vapour, using as the top into
A part of material.For example, by the first product stream from the second conveying pipeline 4, the circulation hydrocarbon stream from recycle hydrocarbons pipeline 6 and Lai
Top feed composed by water vapour from steam pipe line 10 is pushed up after the heating of heated furnace 110 from the second reactor 102
Portion's charging.
In a preferred embodiment, described device further includes waste heat recovery unit 103, for making wait enter described point
The second product stream from unit 104 is respectively with the desalted water for producing the vapor and wait be sent into the first reactor
The methanol charging heat exchange cooling from the second cooler 109 at 101 tops；The vapor that the steam pipe line 10 conveys comes from institute
Desalted water is stated successively through the waste heat recovery unit 103 and the heating gained of the heating furnace 110.
When above-mentioned apparatus is run, as shown in Figure 1, be divided into two strands from extraneous methanol feedstock, wherein one methanol is first
It exchanges heat in the second cooler 109 preheating with the first product stream of the first conveying pipeline 5 conveying, subsequently into waste heat recovery unit
103, further heat exchange is warming up to 240~250 DEG C of temperature with the second product stream 9 from the second reactor 102, from top
Into first reactor 101；Another strand of methanol feeds the then shock chilling medium as first reactor 101, from first reactor side
Line 11 enters catalyst bed and participates in reaction, and adjusts the temperature of each catalytic bed, stablizes in set temperature.Gas-phase methanol is first
Each catalyst bed is from top to bottom sequentially entered in reactor 103, dehydration occurs, and produces dimethyl ether.From first reactor
101 about 340~380 DEG C of temperature of the first product streams come out, are divided into three strands, wherein the first product circulation of accounting 8-15wt%
Cross the conveying of the second conveying pipeline 4, accounting 55-65wt% the first product stream by third conveying pipeline 3, remaining passes through the first conveying pipeline
5 conveyings.
The first product stream through the conveying of the second conveying pipeline 4 is first mixed with the circulation hydrocarbon stream from the first cooler 108, later
The process steam heated with the heated furnace 110 from steam pipe line 10 mixes again, obtains the top feed, subsequently into
Heating furnace 110 from top enters 102 first catalyst bed of second reactor after being heated to 430~470 DEG C.
The first product stream sent through third conveying pipeline defeated 3 successively with the cold dimethyl ether from the top of dimethyl ether knockout tower 107
The mixing of the methanol/water of gas and bottom, each catalyst bed of second reactor 102 is entered from side line 7.Through the first conveying pipeline 5
First product stream of conveying successively exchanges heat with the circulation hydrocarbon stream from recycle hydrocarbons pipeline 6 in the first cooler 108 and cools down, and
It is cooled in the second cooler 109 with material benzenemethanol heat exchange, finally entering refrigerated separation in dimethyl ether knockout tower 107 is gas-liquid
Two-phase, wherein gaseous stream is rich in dimethyl ether, and liquid phase is rich in process water and part unreacted methanol.Gas-liquid two-phase is all used as second
The side entry feed of reactor 102, wherein the liquid phase stream from knockout tower passes through before entering second reactor charging side line 7
Air-cooled processing adjusts temperature to 65 DEG C hereinafter, such as 45-60 DEG C, and gas liquid ratio is determined by the cooling capacity that side entry feed needs, with tune
Each reaction bed temperature is controlled to stablize in range of set value.
Desalted water from battery limit (BL) is after residual neat recovering system 103 and heating furnace 110 heat and from the second conveying pipeline 4
The first product stream and circulation hydrocarbon stream mixing from recycle hydrocarbons pipeline 6 after be warming up to predetermined temperature through heating furnace 110 and enter the
Two reactors 102 carry out propylene reaction processed.
In second reactor 102, gas phase dimethyl ether, methanol and recycle hydrocarbons from top to bottom sequentially enter each catalyst bed
Series reaction, C2-C6 low-carbon alkene and other C1-C10 alkane for being converted into based on propylene etc. occur for layer.Reactor product
Propylene, ethylene, C6+ are obtained by a series of separation, rectifying in separative unit 104, the products such as dry gas and LPG separate simultaneously
Gained C2 and C5-6 recycle hydrocarbons and C4 hydrocarbon, wherein C2 and C5-6 hydrocarbon is some or all of is used as first circulation hydrocarbon stream through recycling
Hydrocarbon pipeline 6 returns to second reactor 102, and the reaction was continued, and C4 hydrocarbon enters four rectifying column 105 of carbon, and most of iso-butane is divided from tower top
It separates out, bottom stream is some or all of, and as second circulation hydrocarbon stream, (iso-butane content is not less than 15%, preferably not less than
5%) second reactor 102 is returned after mixing with first circulation hydrocarbon stream 16 and is continued to participate in reacts, to further increase propene yield,
Reducing influences the yield of propylene because catalyst activity is excessively high.
The present invention is described in detail with reference to embodiments.
It is embodiment in CN104556134A that catalyst is loaded in following embodiment and comparative example, in the second reactor
The HZSM-5 molecular sieve catalyst of 3 preparations.
Embodiment 1
It is tested using simulator as shown in Figure 1, wherein catalysis in first reactor 101 (i.e. DME reactor)
Agent is γ-Al2O3(the DME-1 type catalyst for selecting Clariant Co., Ltd), point two layers of filling.In the second reactor 102
If being of five storeys catalyst bed 9, catalyst is uniformly loaded to the first to the 5th catalyst bed of the second reactor 102,
In spacing upper right between each catalyst bed (any Intermediate Catalyst bed and adjacent catalyst below are incrementally increased under
Spacing is 1.1 times of spacing between its top adjacent catalyst bed layer between bed).
Wherein, the fresh methanol inlet amount of the first reactor 101 is 2.5kg/h, and in the first reactor
The filling total amount of catalyst is 1.8kg, reaction pressure 0.8MPa.The fresh methanol for accounting for total amount 60wt% is preheated to about 270
After DEG C, enter from first reactor top, remaining methanol not preheated (temperature is about 35 DEG C) is fed directly to first reactor
Second catalyst bed.
By in the first obtained product stream, the first product stream of accounting (12 ± 1) wt% by the conveying of the second conveying pipeline 4,
(about 360 DEG C) of the first product stream of accounting (60 ± 1) wt% are conveyed by third conveying pipeline 3, remaining is defeated by the first conveying pipeline 5
It send.
The filling total amount of catalyst is 2.2kg, reaction pressure 0.09MPa in the second reactor.It will send to described
The material of first catalyst bed of two reactors is sent into second reactor after being preheating to about 470 DEG C, in addition, coming from four rectifying of carbon
For the control of iso-butane content in about 5 ± 0.5wt%, the liquid phase from knockout tower 107 is further in the second circulation hydrocarbon stream of tower 105
Control temperature 60 ± 2 DEG C (it will be appreciated by those skilled in the art that in actual motion, the above individual parameters can have certain fluctuation,
Therefore it is indicated in the form of value range).Experimental result is shown in Table 1.
Embodiment 2
The difference from embodiment 1 is that by the first obtained product stream, the first product stream of accounting (10 ± 1) wt%
It is conveyed by the first product stream of the conveying of the second conveying pipeline 4, accounting (57 ± 1) wt% by third conveying pipeline 3, remaining passes through the
The conveying of one conveying pipeline 5.Liquid phase from knockout tower 107 further controls temperature at 55 ± 2 DEG C.Meanwhile in second reactor 102
Spacing is between its top adjacent catalyst bed layer between any Intermediate Catalyst bed and below adjacent catalyst bed
1.2 times of spacing.Experimental result is shown in Table 1.
Comparative example 1
The difference from embodiment 1 is that C4 hydrocarbon stream is all recycled, the catalyst bed interval in second reactor 102
Uniformly.Experimental result is shown in Table 1.
Comparative example 2
The difference from embodiment 1 is that the catalyst bed interval in second reactor 102 is uniform, the first conveying is come from
The material of pipe 5 (about 160 ± 5 DEG C) before entering knockout tower 107 is incorporated to third conveying pipeline 3.Experimental result is shown in Table 1.
Table 1
Claims (9)
1. a kind of preparing propylene from methanol device, which is characterized in that described device includes:
First reactor, for carrying out preparing dimethyl ether from methanol reaction, to obtain the first product stream；
It is respectively used to the first conveying pipeline, the second conveying pipeline and third conveying pipeline of the first product stream of transport portion；
Cooling unit, for being cooled down to the first product stream from first conveying pipeline；
Dimethyl ether knockout tower, for being separated to the first product stream from the cooling unit, in dimethyl ether knockout tower
The rich dimethyl ether gaseous stream that top is isolated, obtains liquid phase stream in bottom；
Second reactor, for carrying out the reaction of the first product stream propylene, to obtain the second product stream；In the second reactor
It is equipped with multiple catalyst beds along longitudinal direction, and further respectively has second reactor feed side between adjacent catalyst bed
Line, the second reactor feed the side line top and bottom with the third conveying pipeline and the dimethyl ether knockout tower respectively
Portion's connection, for will the first product stream from the third conveying pipeline and at least portion from the dimethyl ether knockout tower
Divide gaseous stream and at least partly liquid phase stream is sent into the second reactor；
Separative unit, for being separated to second product stream, rectifying, to isolate C4 hydrocarbon stream, as first circulation hydrocarbon
C2 the and C5-C6 hydrocarbon stream and C3 hydrocarbon stream of stream；
Four rectifying column of carbon, for carrying out rectifying separation to the C4 hydrocarbon stream, to isolate C4 alkane in tower top in tower bottom
Obtain the C4 rich olefins as second circulation hydrocarbon stream；
Recycle hydrocarbons pipeline, for receiving at least partly described first circulation hydrocarbon stream and at least partly described second circulation hydrocarbon stream, with
A part of top feed as the second reactor；
Steam pipe line, for conveying water vapour, using a part of the top feed as the second reactor；
Heating furnace, for from second conveying pipeline, recycle hydrocarbons pipeline and steam pipe line wait enter second reactor top
The mixed material in portion is heated, using the top feed as second reactor.
2. device as described in claim 1, which is characterized in that described device further includes waste heat recovery unit, for make into
Enter the second product stream of the separative unit respectively with the desalted water for producing the vapor and wait be sent into described first
The methanol charging heat exchange cooling of reactor head；The steam pipe line is successively recycled through the waste heat for conveying the desalted water
Unit and the obtained vapor of the heating stove heating.
3. device as claimed in claim 2, which is characterized in that be equipped with multiple catalyst beds in the first reactor along longitudinal direction
Layer, and first reactor charging side line is additionally provided between adjacent catalyst bed, the first reactor feeds side line
For methanol to be fed to the first reactor.
4. device as claimed in claim 3, which is characterized in that the cooling unit includes that the first cooler and second are cooling
Device, first cooler are used to make via the first product stream of first conveying pipeline conveying and via the recycle hydrocarbons pipeline
The circulation hydrocarbon stream of conveying, which exchanges heat, to cool down；Second cooler is used to make to produce via the first of first cooler heat exchange cooling
Logistics further cools down with the methanol charging heat exchange wait be sent into the waste heat recovery unit.
5. such as device of any of claims 1-4, which is characterized in that urged in the first reactor equipped with layer 2-3
Agent bed；
4-8 layers of catalyst bed are equipped in the second reactor, it is preferable that any Intermediate Catalyst of the second reactor
Spacing is the 1.1-1.2 of the spacing between its top adjacent catalyst bed layer between bed and below adjacent catalyst bed
Times.
6. a kind of method of preparing propylene from methanol, which is characterized in that carry out first using the device of any of claims 1-5
The reaction of alcohol propylene；Wherein, the first product stream of the accounting 8-15wt% from first reactor enters the second conveying pipeline, accounting
The first product stream of 55-65wt% enters third conveying pipeline and remaining first product stream enters the first conveying pipeline.
7. according to the method described in claim 6, it is characterized in that, the C4 hydrocarbon stream is all sent into four rectifying column of carbon, abjection
Iso-butane obtains C4 rich in olefin component, and the C4 is not more than 15wt% rich in iso-butane content in olefin component, preferably less
In 5wt%.
8. device and method according to claim 6 or 7, which is characterized in that the liquid phase from the dimethyl ether knockout tower
Logistics controls temperature to 65 DEG C before entering second reactor charging side line hereinafter, it is preferred that control temperature is to 45-60 DEG C.
9. device and method a method according to any one of claims 6-8, which is characterized in that the methanol of the first reactor
Charging is divided into first burst of methanol charging and second burst of methanol charging；Wherein, first strand of methanol charging accounts for the methanol charging
50wt%~70wt%, sent after being preheated to 260 DEG C~300 DEG C first counted from the top down into the first reactor be catalyzed
Agent bed；Second strand of methanol charging is not preheated, is sent respectively from the first reactor side to remaining catalyst bed；
The tower top feeding temperature of the second reactor is 430~470 DEG C.
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