CN102463086A - Reaction device for co-producing low-carbon olefin and p-xylene - Google Patents
Reaction device for co-producing low-carbon olefin and p-xylene Download PDFInfo
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- CN102463086A CN102463086A CN2010105528449A CN201010552844A CN102463086A CN 102463086 A CN102463086 A CN 102463086A CN 2010105528449 A CN2010105528449 A CN 2010105528449A CN 201010552844 A CN201010552844 A CN 201010552844A CN 102463086 A CN102463086 A CN 102463086A
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a reaction device for co-producing low-carbon olefin and p-xylene, which is used for mainly solving the problem of lower yield of low-carbon olefin and p-xylene in the prior art. The problem is well solved by adopting the technical scheme as follows: the reaction device disclosed by the invention mainly comprises a first reaction zone 3, a second reaction zone 4, a third reaction zone 8, a gas-solid separation zone 5 and a regeneration zone 18 of a regenerator; the top of the first reaction zone 3 is connected with the second reaction zone 4; the outlet of the second reaction zone 4 is connected with the gas-solid separation zone 5; a product outlet 14 is arranged on the top of the gas-solid separation zone 5; the bottom of the gas-solid separation zone 5 is connected with the third reaction zone 8; the bottom of the third reaction zone 8 is connected with a stripping zone 11; the bottom of the stripping zone 11 is connected with the regeneration zone 18 of the regenerator through a spent catalyst inclined pipe 13; the bottom of the regeneration zone 18 of the regenerator is connected with a degassing zone 16; and the bottom of the degassing zone 16 is connected with the first reaction zone 3 through a regeneration catalyst inclined pipe 23. The reaction device for co-producing the low-carbon olefin and the p-xylene disclosed by the invention can be used in industrial production of the low-carbon olefin and the p-xylene.
Description
Technical field
The present invention relates to the reaction unit of a kind of co-producing light olefins and paraxylene.
Background technology
Low-carbon alkene, promptly ethene and propylene are two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce through petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, One type of important alternative materials that is used for low-carbon alkene production is an oxygenatedchemicals; For example alcohols (methyl alcohol, ethanol), ethers (dimethyl ether, ethyl methyl ether), ester class (dimethyl carbonate, methyl formate) etc., these oxygenatedchemicals can be transformed through coal, natural gas, living beings equal energy source.Some oxygenatedchemicals can reach fairly large production, like methyl alcohol, can be made by coal or natural gas, and technology is very ripe, can realize up to a million tonnes production scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) receives increasing attention.
Xylenes is important base stock, especially paraxylene.Paraxylene is the base stock of synthesizing polyester (PET), and toluene, C are mainly adopted in paraxylene production at present
9Aromatic hydrocarbons and mixed xylenes are raw material, prepare through disproportionation, isomerization, adsorbing separation or cryogenic separation.Because the paraxylene content in its product is controlled by thermodynamics, paraxylene is at C
8Only account for approximately 24% in the BTX aromatics, solid circulating rate is very big in the technical process, and operating cost is higher.In recent years, the lot of domestic and international patent discloses a lot of variation routes of preparation paraxylene, wherein, is paid much attention to through the technology that methylation reaction prepares paraxylene by methyl alcohol and toluene.Because the boiling point of three isomers differs very little in the xylenes, through the highly purified paraxylene of the very difficult acquisition of the distillation technique of routine.The selectivity of the raising paraxylene that therefore need in the process of preparation xylenes, try one's best.
After nineteen seventies ZSM-5 synthesizes successfully,, cause extensive attention because this catalyst all has unique catalytic performance to many reactions such as alkylation, isomerization, phenyl ring methylate.
Mobil company in 1976 discloses methyl alcohol is converted into hydrocarbon at the ZSM-5 molecular sieve catalyst reaction.Disclose methyl alcohol among the USP4542252 and on the ZSM-5 molecular sieve catalyst, produced the method for low-carbon alkene; Disclose among USP 3944041, USP4049573, USP 4100219, EP6501, the JP 60126233 and used the alkali metal modified ZSM-5 catalyst to be used for the reaction of preparing low carbon olefinic hydrocarbon with methanol; Disclose among the USP 5367100 and used the reaction that methyl alcohol prepares low-carbon alkene on phosphorus and the lanthanum modified ZSM-5 catalyst, the overall selectivity of its ethene, propylene and butylene can reach about 82%.
The pore canal system that the ZSM-5 zeolite is made up of 10 yuan of rings; Have medium sized aperture and aperture; Not only can allow the rapid diffusion of methyl alcohol or low-carbon alkene; Can also allow molecular diameter is that the paraxylene of 0.63 nanometer spreads rapidly, can effectively hinder ortho-xylene that molecular diameter is 0.69 nanometer simultaneously, ask the xylenes diffusion.This fact means carries out the possibility that shape is selected to toluene phenyl ring methylation reaction, can obtain to be higher than in the xylenes product paraxylene content of thermodynamical equilibrium concentration far away.
CN1326430 discloses the method that a kind of alkylated aromatic hydrocarbons reactant is produced alkylation aromatic products, and especially for the methanol toluene methylation reaction, its characteristic mainly is to have adopted the method that toluene, methyl alcohol are introduced reactor in different positions to prepare xylenes.CN1355779 discloses the method that a kind of direct selective synthesizing becomes paraxylene, the aromatic compound through will comprising toluene, benzene and composition thereof with by CO, CO
2, H
2And composition thereof the methylating reagent reaction formed, this method makes at least 5% aromatic compound be converted into xylene mixture, wherein paraxylene accounts at least 30% of xylene mixture.
CN1231653 discloses the method that a kind of selectivity is made paraxylene, and on the catalyst that a kind of porous crystalline material is processed, this catalyst comprises the oxide that ZSM-5 or ZSM-11 zeolite and modification use, with methyl alcohol and toluene prepared in reaction paraxylene.CN1775715 discloses a kind of method for preparing the xylenes product, uses a kind of ZSM-5 zeolite ability catalyst of phosphorous modification, toluene, methyl alcohol, hydrogen are introduced reactor, but the toluene conversion in this method is on the low side, and the highest only have 23%.CN1759081 discloses a kind of method for preparing paraxylene; Adopt the ZSM-5 zeolite catalyst of oxide modifying, in flow reactor, operation under high linear speed; Reactant and catalyst time of contact were less than 1 second; Can improve the paraxylene selectivity, but the toluene conversion of this method is on the low side, the highest only have 22%.
The method that a kind of toluene and methylating reagent prepare paraxylene and co-producing light olefins is disclosed among the CN 101456786; Use has the alumino-silicate or the silicoaluminophosphate zeolite molecular sieve of MFI, MEL or AEL crystallization skeleton structure; Through rare-earth metal modified; Fluid catalyst is prepared in spray-dried moulding, is used for toluene and methylating reagent prepares paraxylene, simultaneously co-producing light olefins.But because this method only adopts a reactor to prepare paraxylene and co-producing light olefins simultaneously, the C1-C5 product that is obtained is the highest to have only 23.72%, and there is the lower problem of propene yield in propene yield less than 10%.
Prior art all exists low-carbon alkene (especially propylene) and the lower problem of paraxylene yield; And not solving the coupled problem of methanol-to-olefins reaction, methyl alcohol and two technologies of toluene methylation system paraxylene on same catalyst preferably, the present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is low-carbon alkene (especially propylene) and the lower problem of paraxylene yield that exists in the prior art, and a kind of new co-producing light olefins and the reaction unit of paraxylene are provided.This device is used for the production of low-carbon alkene and paraxylene, has low-carbon alkene (especially propylene) yield and paraxylene yield advantage of higher.
For addressing the above problem; The technical scheme that the present invention adopts is following: the reaction unit of a kind of co-producing light olefins and paraxylene; Comprise that mainly first reaction zone 3, second reaction zone 4, the 3rd reaction zone 8, gas solid separation district 5, regenerator renewing zone 18, stripping zone 11, degas zone 16, the first reaction zones 3 tops link to each other with second reaction zone 4,4 outlets of second reaction zone link to each other with gas solid separation district 5; 5 inside, gas solid separation district are provided with gas-solid cyclone separator 7; The top has products export 14, and the bottom links to each other with the 3rd reaction zone 8, and the 3rd reaction zone 8 bottoms link to each other with stripping zone 11; Stripping zone 11 bottoms have catalyst outlet and link to each other with regenerator renewing zone 18 through reclaimable catalyst inclined tube 13; 18 bottoms, regenerator renewing zone link to each other with degas zone 16, and degas zone 16 bottoms have catalyst outlet and link to each other with first reaction zone 3 through regenerated catalyst inclined tube 23, and the 3rd reaction zone 8 bottoms have catalyst outlet and link to each other with second reaction zone 4 through inclined tube 10.
In the technique scheme, said catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is 20～200; Said the 3rd reaction zone is dense-phase fluidized bed, turbulent fluidized bed or fast fluidized bed; Said regenerator renewing zone is a dense-phase fluidized bed; Said first reaction zone 3 bottoms are provided with buffering 2, the second reaction zones, 4 bottoms, mixed zone and are provided with the quick separation equipment 6 of gas-solid; Said stripping zone 11 stripping media are steam, and the degassing medium of degas zone 16 is nitrogen or steam; Comprise carbon four hydrocarbon in said feeding line 1 charging, comprise methyl alcohol and toluene in feeding line 24 chargings, feeding line 9 chargings are mainly methyl alcohol.
The reaction temperature of first reaction zone according to the invention is 500～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～12 meter per seconds; The reaction temperature of said second reaction zone is 380～450 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 1.0～2.0 meter per seconds; The reaction temperature of said the 3rd reaction zone is 400～470 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 0.3～2.0 meter per second.
The computational methods of average coke content according to the invention are that carbon deposit quality on the catalyst of certain mass is divided by described catalyst quality.Carbon deposit measuring method on the catalyst is following: will mix the catalyst mix that has carbon deposit comparatively uniformly; The accurate carbon-bearing catalyst of weighing certain mass then; Be put in the pyrocarbon analyzer and burn; Through the carbon dioxide quality of infrared analysis burning generation, thereby obtain the carbonaceous amount on the catalyst.
Toluene conversion of the present invention, methanol conversion, C1-C5 hydrocarbon butt yield, paraxylene yield, total aromatic hydrocarbons butt yield, low-carbon alkene butt yield computational methods are:
Toluene conversion, toluene quality/methylbenzene raw material quality * 100% in the %=100-product;
Methanol conversion, the methanol quality in the %=100-product/methanol feedstock quality * 100%;
C1-C5 hydrocarbon butt yield, C1-C5 quality in the %=product/(methanol feedstock quality * 0.4375) * 100%;
The paraxylene yield, the quality of paraxylene/methylbenzene raw material quality * 100% in the %=product;
Low-carbon alkene butt yield, the quality of low-carbon alkene in the %=product/(methanol feedstock quality * 0.4375) * 100%;
Total aromatic hydrocarbons butt yield, the gross mass of aromatic hydrocarbons in the %=product/(methanol feedstock quality * 0.4375+ methylbenzene raw material quality) * 100%;
ZSM-5 catalyst of the present invention is to be active main body with the ZSM-5 molecular sieve, adopt add binding agent after method spray-dried, the roasting moulding prepare.The binding agent that adds can make SiO
2Or Al
2O
3, the addition of binding agent is counted between 10～80% with its percentage in moulding rear catalyst quality.The catalyst of moulding for example adopts the polysiloxanes of phenyl methyl polysiloxanes to select the shape processing.
Because the pore passage structure that the ZSM-5 catalyst is unique can carry out the reaction of preparing light olefins from methanol and toluene methylation simultaneously.Adopt reaction unit of the present invention; Three reaction zones are set; Carbon four, carbon five hydro carbons that first reaction zone is used for conversion by-product under higher temperature are low-carbon alkene; Second reaction zone is mainly used in toluene methylation and prepares paraxylene, and the product (like ethene) of the part methyl alcohol and first reaction zone continues the reaction propylene enhancing simultaneously, and the 3rd reaction zone is mainly used in methanol-to-olefins reaction.The carbon distribution that forms on the first reaction zone catalyst help improving toluene methylation shape selectivity can, and the carbon distribution of performance helps the production low-carbon alkene of the 3rd reaction zone methyl alcohol high selectivity on the second reaction zone catalyst.The existence of hydro carbons such as alkene, alkane also can help improving the yield of xylenes for methylating the supply methyl basically in second reaction zone, and adopts fast fluidized bed, helps paraxylene and optionally improves.Therefore, adopt reaction unit of the present invention, can adjust the product mix flexibly, have low-carbon alkene (especially propylene) and paraxylene yield advantage of higher simultaneously through the charge proportion of methyl alcohol and toluene.
Adopt technical scheme of the present invention: said catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is 20～200; Said the 3rd reaction zone is dense-phase fluidized bed, turbulent fluidized bed or fast fluidized bed; Said regenerator renewing zone is a dense-phase fluidized bed; Said first reaction zone 3 bottoms are provided with buffering 2, the second reaction zones, 4 bottoms, mixed zone and are provided with the quick separation equipment 6 of gas-solid; Said stripping zone 11 stripping media are steam, and the degassing medium of degas zone 16 is nitrogen or steam; Comprise carbon four hydrocarbon in said feeding line 1 charging, comprise methyl alcohol and toluene in feeding line 24 chargings, feeding line 9 chargings are mainly methyl alcohol; Toluene conversion reaches more than 37%, and methanol conversion reaches more than 99%, and C1-C5 hydrocarbon butt yield reaches more than 49%; Total aromatic hydrocarbons butt yield reaches more than 58%, and the paraxylene yield reaches more than 36%, and low-carbon alkene butt yield reaches more than 89%; Wherein propylene butt yield reaches more than 65%, has obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the bottom first raw material charging of first reaction zone; 2 is buffering mixed zone, first reaction zone bottom; 3 is first reaction zone; 4 is second reaction zone; 5 is the gas solid separation district; 6 are the quick separation equipment of gas-solid; 7 is gas-solid cyclone separator; 8 is the 3rd reaction zone; 9 is the 3rd reaction zone the 3rd material feeding tube line; 10 is that the 3rd reaction zone catalyst advances the second reaction zone inclined tube; 11 is stripping zone; 12 is the stripped vapor pipeline; 13 is the reclaimable catalyst inclined tube; 14 is the product outlet line; 15 are degassing medium pipeline; 16 is degas zone; 17 is the regenerating medium suction line; 18 is the regenerator renewing zone; 19 is the regenerated flue gas outlet line; 20 is gas-solid cyclone separator; 21 is the 3rd reaction zone heat collector; 22 is the regenerator external warmer; 23 is the regenerated catalyst inclined tube; 24 is the second raw material charging.
The 3rd raw material gets in the 3rd reaction zone 8 through feeding line 9, contacts with molecular sieve catalyst, and reaction generates the product stream I that contains low-carbon alkene, and decaying catalyst gets into regenerator 18 regeneration from reclaimable catalyst inclined tube 13.Catalyst after regeneration is accomplished gets into the catalyst buffering area 2 of first reaction zone, 3 bottoms from regenerated catalyst inclined tube 23; Contact back entering first reaction zone 3 with first raw material from pipeline 1; The product and the catalyst of 3 outlets of first reaction zone get in second reaction zone 4; Contact with second raw material, generate low-carbon alkene product stream II, product stream II and catalyst get into gas solid separation district 5; Product stream II and product stream I are mixed into centrifugal station, and isolated catalyst gets into the 3rd reaction zone 8 and continues to participate in reaction.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is that 20, the first raw materials get into first reaction zone, contacts with catalyst; Wherein first raw material comprises that mass fraction is 60% carbon four hydrocarbon mixtures, 26% carbon five hydrocarbon mixtures, and all the other are steam, and said carbon four, carbon five hydrocarbon mixtures are the byproduct of methanol conversion; Gaseous stream and catalyst that first reaction zone generates get into second reaction zone, contact with second raw material of toluene with comprising methyl alcohol, and wherein the weight ratio of methyl alcohol and toluene is 1: 5 in second raw material; The second raw materials quality flow is 2 kilograms/hour, and the gaseous stream that second reaction zone generates gets into the gas solid separation district with catalyst after the quick separation equipment of gas-solid separates, and isolated gaseous stream gets into centrifugal station; Isolated catalyst gets into the 3rd reaction zone, contacts with the 3rd raw material, and wherein the 3rd raw material is that purity is 99.5% methyl alcohol; Generation comprises the product of low-carbon alkene, forms carbon deposition catalyst simultaneously, and carbon deposition catalyst is divided into two parts; Wherein 70% return second reaction zone; 30% gets into regenerator regeneration behind the steam stripping, form regenerated catalyst, and regenerated catalyst returns first reaction zone after the steam degassing then.First reaction zone is a riser, and second reaction zone is a fast fluidized bed, and the 3rd reaction zone is a dense-phase fluidized bed, and regenerator is a dense-phase fluidized bed.The average carbon deposition quantity mass fraction of said carbon deposition catalyst is 0.5%, and the average carbon deposition quantity mass fraction of regenerated catalyst is 0.01%.The reaction temperature of first reaction zone is 500 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 4 meter per seconds; The reaction temperature of second reaction zone is 380 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 1.0 meter per seconds; The reaction temperature of the 3rd reaction zone is 400 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 0.3 meter per second.The total methanol feeding amount of this reaction unit and the weight ratio of toluene feed amount are 2.5: 1.Gas-liquid phase product adopts gas chromatographic analysis; Analysis result is: toluene conversion is 37.21%, and methanol conversion is 98.73%, and C1-C5 hydrocarbon butt yield is 42.68%; Total aromatic hydrocarbons butt yield is 55.49%; The paraxylene yield is 35.41%, and low-carbon alkene butt yield is 86.79%, and wherein propylene butt yield is 63.58%.
[embodiment 2]
According to embodiment 1 described condition and step, catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is that 200, the first raw materials get into first reaction zone, contacts with catalyst; Wherein first raw material comprises that mass fraction is 48% carbon four hydrocarbon mixtures, 37% carbon five hydrocarbon mixtures, and all the other are steam, and said carbon four, carbon five hydrocarbon mixtures are the byproduct of methanol conversion; Gaseous stream and catalyst that first reaction zone generates get into second reaction zone, contact with second raw material of toluene with comprising methyl alcohol, and wherein the weight ratio of methyl alcohol and toluene is 1: 3 in second raw material; The second raw materials quality flow is 2.7 kilograms/hour, and the gaseous stream that second reaction zone generates gets into the gas solid separation district with catalyst after the quick separation equipment of gas-solid separates, and isolated gaseous stream gets into centrifugal station; Isolated catalyst gets into the 3rd reaction zone, contacts with the 3rd raw material, and wherein the 3rd raw material is that purity is 99.5% methyl alcohol; Generation comprises the product of low-carbon alkene, forms carbon deposition catalyst simultaneously, and carbon deposition catalyst is divided into two parts; Wherein 40% return second reaction zone; 60% gets into regenerator regeneration behind the steam stripping, form regenerated catalyst, and regenerated catalyst returns first reaction zone after the steam degassing then.First reaction zone is a riser, and second reaction zone is a fast fluidized bed, and the 3rd reaction zone is a fast fluidized bed, and regenerator is a dense-phase fluidized bed.The average carbon deposition quantity mass fraction of said carbon deposition catalyst is 2.5%, and the average carbon deposition quantity mass fraction of regenerated catalyst is 0.3%.The reaction temperature of first reaction zone is 600 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 12 meter per seconds; The reaction temperature of second reaction zone is 450 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 2.0 meter per seconds; The reaction temperature of the 3rd reaction zone is 470 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 2.0 meter per seconds.The total methanol feeding amount of this reaction unit and the weight ratio of toluene feed amount are 3.34: 1.Gas-liquid phase product adopts gas chromatographic analysis; Analysis result is: toluene conversion is 37.63%, and methanol conversion is 99.81%, and C1-C5 hydrocarbon butt yield is 46.88%; Total aromatic hydrocarbons butt yield is 52.05%; The paraxylene yield is 36.71%, and low-carbon alkene butt yield is 88.04%, and wherein propylene butt yield is 65.29%.
[embodiment 3]
According to embodiment 1 described condition and step, catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is that 100, the first raw materials get into first reaction zone, contacts with catalyst; Wherein first raw material comprises that mass fraction is 54% carbon four hydrocarbon mixtures, 31% carbon five hydrocarbon mixtures, and all the other are steam, and said carbon four, carbon five hydrocarbon mixtures are the byproduct of methanol conversion; Gaseous stream and catalyst that first reaction zone generates get into second reaction zone, contact with second raw material of toluene with comprising methyl alcohol, and wherein the weight ratio of methyl alcohol and toluene is 1: 2 in second raw material; The second raw materials quality flow is 2 kilograms/hour, and the gaseous stream that second reaction zone generates gets into the gas solid separation district with catalyst after the quick separation equipment of gas-solid separates, and isolated gaseous stream gets into centrifugal station; Isolated catalyst gets into the 3rd reaction zone, contacts with the 3rd raw material, and wherein the 3rd raw material is that purity is 99.5% methyl alcohol; Generation comprises the product of low-carbon alkene, forms carbon deposition catalyst simultaneously, and carbon deposition catalyst is divided into two parts; Wherein 50% return second reaction zone; 50% gets into regenerator regeneration behind the steam stripping, form regenerated catalyst, and regenerated catalyst returns first reaction zone after the steam degassing then.First reaction zone is a riser, and second reaction zone is a fast fluidized bed, and the 3rd reaction zone is a turbulent fluidized bed, and regenerator is a dense-phase fluidized bed.The average carbon deposition quantity mass fraction of said carbon deposition catalyst is 1.2%, and the average carbon deposition quantity mass fraction of regenerated catalyst is 0.1%.The reaction temperature of first reaction zone is 550 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 7 meter per seconds; The reaction temperature of second reaction zone is 425 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 1.5 meter per seconds; The reaction temperature of the 3rd reaction zone is 450 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 0.8 meter per second.The total methanol feeding amount of this reaction unit and the weight ratio of toluene feed amount are 5: 1.Gas-liquid phase product adopts gas chromatographic analysis; Analysis result is: toluene conversion is 33.04%, and methanol conversion is 98.28%, and C1-C5 hydrocarbon butt yield is 49.04%; Total aromatic hydrocarbons butt yield is 48.79%; The paraxylene yield is 32.11%, and low-carbon alkene butt yield is 89.42%, and wherein propylene butt yield is 65.61%.
[embodiment 4]
According to embodiment 2 described condition and steps, catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is that 60, the first raw materials get into first reaction zone, contacts with catalyst; The gaseous stream and the catalyst that generate get into second reaction zone, contact with second raw material of toluene with comprising methyl alcohol, and wherein the weight ratio of methyl alcohol and toluene is 1: 1 in second raw material; The second raw materials quality flow is 2.3 kilograms/hour, and the gaseous stream that second reaction zone generates gets into the gas solid separation district with catalyst after the quick separation equipment of gas-solid separates, and isolated gaseous stream gets into centrifugal station; Isolated catalyst gets into the 3rd reaction zone, contacts with the 3rd raw material, and wherein the 3rd raw material is that purity is 99.5% methyl alcohol; Generation comprises the product of low-carbon alkene, forms carbon deposition catalyst simultaneously, and carbon deposition catalyst is divided into two parts; Wherein 45% return second reaction zone; 55% gets into regenerator regeneration behind the steam stripping, form regenerated catalyst, and regenerated catalyst returns first reaction zone after the steam degassing then.The average carbon deposition quantity mass fraction of said carbon deposition catalyst is 2.0%, and the average carbon deposition quantity mass fraction of regenerated catalyst is 0.08%.The reaction temperature of first reaction zone is 580 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 6 meter per seconds; The reaction temperature of second reaction zone is 430 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 1.25 meter per seconds; The reaction temperature of the 3rd reaction zone is 460 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 0.86 meter per second.Gas-liquid phase product adopts gas chromatographic analysis; Analysis result is: toluene conversion is 34.08%, and methanol conversion is 99.57%, and C1-C5 hydrocarbon butt yield is 39.61%; Total aromatic hydrocarbons butt yield is 58.52%; The paraxylene yield is 32.16%, and low-carbon alkene butt yield is 84.53%, and wherein propylene butt yield is 57.49%.
Obviously, adopt reaction unit of the present invention, can reach the purpose that improves low-carbon alkene and paraxylene yield, have bigger technical advantage, can be used in the commercial production of low-carbon alkene and paraxylene.
Claims (6)
1. the reaction unit of co-producing light olefins and paraxylene; Mainly comprise first reaction zone (3), second reaction zone (4), the 3rd reaction zone (8), gas solid separation district (5), regenerator renewing zone (18), stripping zone (11), degas zone (16); First reaction zone (3) top links to each other with second reaction zone (4); Second reaction zone (4) outlet links to each other with gas solid separation district (5), and inside, gas solid separation district (5) is provided with gas-solid cyclone separator (7), and the top has products export (14); The bottom links to each other with the 3rd reaction zone (8); The 3rd reaction zone (8) bottom links to each other with stripping zone (11), and stripping zone (11) bottom has catalyst outlet and links to each other with regenerator renewing zone (18) through reclaimable catalyst inclined tube (13), and regenerator renewing zone (18) bottom links to each other with degas zone (16); Degas zone (16) bottom has catalyst outlet and links to each other with first reaction zone (3) through regenerated catalyst inclined tube (23), and the 3rd reaction zone (8) bottom has catalyst outlet and links to each other with second reaction zone (4) through inclined tube (10).
2. according to the reaction unit of said co-producing light olefins of claim 1 and paraxylene, it is characterized in that said catalyst is ZSM-5, SiO
2/ Al
2O
3Mol ratio is 20～200.
3. according to the reaction unit of said co-producing light olefins of claim 1 and paraxylene, it is characterized in that said the 3rd reaction zone is dense-phase fluidized bed, turbulent fluidized bed or fast fluidized bed; Said regenerator renewing zone is a dense-phase fluidized bed.
4. according to the reaction unit of said co-producing light olefins of claim 1 and paraxylene, it is characterized in that said first reaction zone (3) bottom is provided with buffering mixed zone (2), second reaction zone (4) bottom is provided with the quick separation equipment of gas-solid (6).
5. according to the reaction unit of said co-producing light olefins of claim 1 and paraxylene, it is characterized in that said stripping zone (11) stripping medium is a steam, the degassing medium of degas zone (16) is nitrogen or steam.
6. according to the reaction unit of said co-producing light olefins of claim 1 and paraxylene, it is characterized in that comprising carbon four hydrocarbon in said feeding line (1) charging that comprise methyl alcohol and toluene in feeding line (24) charging, feeding line (9) charging is mainly methyl alcohol.
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|---|---|---|---|
| CN201010552844.9A CN102463086B (en) | 2010-11-17 | 2010-11-17 | Reaction device for co-producing low-carbon olefin and p-xylene |
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| CN201010552844.9A CN102463086B (en) | 2010-11-17 | 2010-11-17 | Reaction device for co-producing low-carbon olefin and p-xylene |
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Cited By (18)
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| CN103831063A (en) * | 2012-11-23 | 2014-06-04 | 洛阳凯美胜石化设备有限公司 | Online catalyst addition and unloading apparatus |
| CN104437274A (en) * | 2013-09-16 | 2015-03-25 | 中国石油大学(华东) | Fluidized bed reactor used for light olefin cracking and Methanol To Olefin (MTO) |
| CN104437274B (en) * | 2013-09-16 | 2017-01-11 | 中国石油大学(华东) | Fluidized bed reactor used for light olefin cracking and Methanol To Olefin (MTO) |
| CN105498370A (en) * | 2014-10-14 | 2016-04-20 | 中国石油化工股份有限公司 | Separation apparatus, reaction regeneration apparatus, olefin preparation method and aromatic hydrocarbon preparation method |
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| KR102243311B1 (en) | 2016-10-19 | 2021-04-21 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | High-speed fluidized bed reactor, apparatus and method for producing propylene and C4 hydrocarbons from oxygen-containing compounds |
| KR20190062545A (en) * | 2016-10-19 | 2019-06-05 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Process for producing propylene, C4 hydrocarbons and apparatus therefor |
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