CN103588601A - Fluidized bed method for producing p-xylene through shape-selective toluene and methanol alkylation - Google Patents
Fluidized bed method for producing p-xylene through shape-selective toluene and methanol alkylation Download PDFInfo
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- CN103588601A CN103588601A CN201310566312.4A CN201310566312A CN103588601A CN 103588601 A CN103588601 A CN 103588601A CN 201310566312 A CN201310566312 A CN 201310566312A CN 103588601 A CN103588601 A CN 103588601A
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- toluene
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 211
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 106
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 34
- 230000029936 alkylation Effects 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000011069 regeneration method Methods 0.000 claims abstract description 27
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 7
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 229910052755 nonmetal Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 230000002152 alkylating effect Effects 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- AHPIVEJVZPWSEM-UHFFFAOYSA-N methanol;toluene;1,4-xylene Chemical compound OC.CC1=CC=CC=C1.CC1=CC=C(C)C=C1 AHPIVEJVZPWSEM-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a fluidized bed method for producing p-xylene through shape-selective toluene and methanol alkylation, and mainly solves the problem of lower selectivity for p-xylene in the prior art. The fluidized bed method for producing the p-xylene through the shape-selective toluene and methanol alkylation comprises the steps as follows: 1), raw materials enter a reaction zone of a fluidized bed reactor after heated and are contacted with an alkylation catalyst, and a mixture flow of the p-xylene is generated; 2), the mixture flow enters a rapid gas-solid separation zone, a separated gaseous product enters a follow-up separation section, a separated catalyst enters a toluene pre-contact region, at least one part of the catalyst in the toluene pre-contact region enters a regenerator for regeneration after steam stripping by a steam stripping zone, and a regenerated catalyst is formed; and 3), the regenerated catalyst returns to the reaction zone for continuous reaction. With the adoption of the technical scheme, the problem is solved, and the method can be applied to p-xylene production.
Description
Technical field
The present invention relates to a kind of methylbenzene methanol and select the bed process that p-Xylol is produced in type alkylation.
Technical background
As the main raw material of synthetic terephthalic acid and dimethyl terephthalate (DMT), the dimethylbenzene particularly demand of p-Xylol constantly increases.At present, the technique of industrial production p-Xylol mainly comprises toluene disproportionation, aromatic hydrocarbons transalkylation, MTA technique etc. both at home and abroad, all has the problems such as raw material availability is low, dimethylbenzene selective is poor.Adopt toluene-methyl alcohol to select type alkylation p-Xylol technique processed, low yield benzene does not even produce benzene, meets the present situation of domestic benzene glut the market, has effectively promoted methylbenzene raw material utilization ratio.In alkylation process, the selectivity of p-Xylol is high simultaneously, and by product is few, greatly reduces the difficulty of later separation, becomes the mode of production that can substitute above two kinds of techniques.Yet the very easily coking under reaction conditions of the alkylating reagent methyl alcohol of introducing, causes catalyst deactivation, Selectivity for paraxylene variation, solve inactivation problem is the key of alkylation of toluene methanol technical development always.
Adopt fluidized-bed reactor to regenerate in real time to decaying catalyst, reduced side reaction adding of terminator simultaneously, efficiently solve fixed bed reactor catalyst inactivation fast, the problem that Selectivity for paraxylene is low.Patent CN102372585 divides multiply to introduce reactor from one or more positions in fluidized-bed reactor entrance downstream the alkylating reagent containing methyl alcohol, dme, this can make alkylating reagent be uniformly distributed in reactor on the one hand, effectively promotes use ratio of methanol.Yet the ununiformity that alkylating reagent mixes with aromatic hydrocarbons has increased the possibility of himself reaction.Patent CN101417236 discloses the fluid catalyst of a kind of alkylation p-Xylol coproduction processed alkene, and wherein the selectivity of p-Xylol in xylene isomer is greater than 99%, but the life-span of catalyzer is not long.Patent CN102372584 be take dme as alkylating reagent, and benzene, toluene are that aroamtic hydrocarbon raw material carries out alkylated reaction, preferably resolve reaction bed temperature rise large, the problem of poor catalyst stability, but methyl alcohol side reaction is not subject to effective restriction, and Selectivity for paraxylene is lower, is no more than 85%.
In above-mentioned document related technical problem underlying be reactant particularly alkylating reagent methyl alcohol and catalyzer long invalid duration of contact, in time separation or stopped reaction, do not cause side reaction particularly coking reaction increase, the easy inactivation of catalyzer.Simultaneous reactions air speed is lower, and the selectivity of object product is lower.
The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of Selectivity for paraxylene in prior art, provides a kind of new methylbenzene methanol to select the bed process that p-Xylol is produced in type alkylation.The method, for the production of p-Xylol, has advantages of that Selectivity for paraxylene is higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation, comprise following step: the raw material that (1) comprises methyl alcohol and toluene is through the laggard reaction zone that enters fluidized-bed reactor of heating vaporization, contact with alkylation catalyst, generate the mixture flow containing p-Xylol; (2) described mixture flow enters the gas-solid sharp separation district being connected with top, described reaction zone, isolated gas-phase product enters later separation workshop section again after cyclonic separator separation, the isolated catalyzer of gas-solid sharp separation district and cyclonic separator enters the pre-zone of action of toluene, catalyzer at least a portion of the pre-zone of action of toluene enters revivifier regeneration after the stripping of stripping zone, forms regenerated catalyst; (3) described regenerated catalyst returns to reaction zone and proceeds reaction; Wherein, in gas-solid sharp separation district, inject terminator, the weight ratio of terminator and raw material is 1:1～1000, and terminator feeding temperature is 20-300 ℃.
In technique scheme, preferably, described terminator is selected from least one of methyl alcohol, water.
In technique scheme, preferably, the catalyzer of the pre-zone of action of described toluene 5～60% goes revivifier regeneration through inclined tube to be generated by weight, and 40～95% return to reaction zone by catalyzer outer circulating tube after heat exchange.
In technique scheme, preferably, the reaction conditions of described reaction zone is: temperature of reaction is 350-600 ℃, reaction pressure 0.1-5MPa, toluene and methanol mol ratio 0.1-10:1 in charging, catalyzer than 0.1-20:1, can add carrier gas with raw material weight in raw material charging, and described carrier gas is water vapour, H
2, at least one in CO, carrier gas/toluene mole ratio is 0-8:1; Described carrier gas is water vapour, H
2, at least one in CO.
In technique scheme, preferably, described stripping zone stripping medium is water vapour.
In technique scheme, preferably, catalyzer is continuous flow and regeneration in fluidized-bed reactor and revivifier, in revivifier, is contacted burning-off carbon distribution by air with catalyzer, and revivifier regeneration temperature is 560 ℃-680 ℃.
In technique scheme, preferably, described alkylation catalyst comprises at least one in molecular sieve and hydrogenation metal or its oxide compound, rare earth metal or its oxide compound, nonmetal oxide; At least one in ZSM-5, ZSM-11, ZSM-22, ZSM-23, FMI, MCM-22, MCM-56, MCM-49, SAPO-11, EU-1 of molecular screening; Hydrogenation metal is selected from least one in platinum, palladium, nickel, molybdenum, copper, zinc, cobalt; Rare earth metal is selected from lanthanum or cerium; Nonmetal at least one being selected from boron, nitrogen or phosphorus.
In technique scheme, more preferably, the molecular sieve in described alkylation catalyst is ZSM-5, SiO
2/ Al
2o
3mol ratio is 100-500; Hydrogenation metal is platinum, palladium, nickel, molybdenum, cobalt; Nonmetal is boron or phosphorus; Component in described alkylation catalyst is counted with parts by weight: a) 50-80 part ZSM-5 molecular sieve; B) 0.3-4 part hydrogenation metal or oxide compound; C) 1-30 part rare earth metal or its oxide compound; D) 0-10 part nonmetal oxide.
In technique scheme, preferably, in the pre-zone of action of described toluene, pass into comprise toluene logistics as fluidizing medium.
Reaction parameter in the present invention obtains with following formula:
Terminator described in the present invention is selected from least one in methyl alcohol, ethanol, water.
At alkylation of toluene methanol, prepare in p-Xylol technique, alkylating reagent methyl alcohol with catalyzer Long contact time under easily there is coking reaction, cause catalyst deactivation, adopt circulating fluid bed reactor that catalyzer can be regenerated in real time, simultaneous reactions bed temperature distributes more evenly, heat of reaction is effectively spread, and has greatly improved catalytic efficiency and has solved the easy inactivation problem of catalyzer.Yet in the negative area of fluidized-bed reactor, a large amount of unsegregated catalyzer at high temperature can continue and product generation secondary reaction, side reaction is increased, cause object product Selectivity for paraxylene to reduce.The present invention, at the low temperature terminator of gas-solid separator entrance injected water or methyl alcohol, does not introduce other material in reaction system, significantly reduce the temperature of catalyzer and reaction mixture, and reactor temperature rise is reduced.And temperature is to control the key of reaction, maintain temperature stably and both guaranteed carrying out smoothly of alkylation main reaction, make again side reaction reduce, effectively improved the selectivity of object product.Simultaneously, catalyzer after gas solid separation enters the pre-zone of action of toluene, toluene is fully adsorbed in the duct of catalyzer, when contact alkylating reagent methyl alcohol, can highly selective, be converted into p-Xylol fast, meet the short requirement that needs to accelerate rate of mass transfer duration of contact of fluidized-bed reactor agent material.Adopt fluidized-bed reactor of the present invention for alkylation of toluene methanol p-Xylol technique processed, in temperature of reaction, be 350-600 ℃, reaction pressure 0.1-5MPa, charging toluene and methanol mol ratio 0.1-10:1, catalyzer is with raw material weight than 0.1-20, and carrier gas/toluene mole ratio is under 0-8 condition, and toluene conversion can reach more than 30%, the selectivity of p-Xylol in dimethylbenzene can reach more than 95%, obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the reaction-regeneration system schematic flow sheet of the method for the invention.
1 is the charging of methanol toluene raw material and carrier gas; 2 is catalyzer outer circulating tube; 3 is interchanger; 4 is gas-solid sharp separation district; 5 is fast gas-solid separator; 6 is settling vessel; 7 is airway; 8 is cyclonic separator; 9 is collection chamber; 10 is gaseous product outlet; 11 is stripping zone; 12 is water stripping vapor feed pipeline; 13 is toluene feed pipeline; 14 is inclined tube to be generated; 15 is revivifier; 16 is cyclonic separator; 17 is regenerator flue gas outlet; 18 is regenerator sloped tube; 19 is terminator injection pipeline; 20 is the pre-zone of action of toluene; 21 is regeneration air pipeline; 22 is fluidized-bed reactor reaction zone.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, take water as terminator, terminator temperature is 25 ℃, Wei Ju gas solid separation district, terminator injection phase bottom level is 1/10 of gas solid separation district riser tube height, raw material and terminator mol ratio are 15:1, and catalyzer is ZSM-5, SiO
2/ Al
2o
3mol ratio is 100, and loaded metal is 0.5wt%Pd, 8wt%La
2o
3, 5wt%P
2o
5.Methylbenzene methanol raw material mixes after vaporizing respectively, after heat exchange preheating, from fluidized-bed reactor bottom, enter, in reaction zone, contact with alkylation catalyst, the mixture of p-Xylol is rich in generation, reaction conditions is: 420 ℃ of temperature of reaction, and reaction pressure is counted 0.1Mpa with gauge pressure, and catalyzer compares 0.5:1 with raw material weight, methanol/toluene mol ratio=1:2, hydrogen/toluene mole ratio is 2:1.Revivifier regeneration temperature is 650 ℃, the pre-zone of action of toluene passes into toluene as fluidizing medium, the pre-zone of action of toluene linear speed is 0.15m/s, and the catalyzer of the pre-zone of action of toluene 50% goes revivifier regeneration through inclined tube to be generated by weight, and 50% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 31.2%, and dimethylbenzene selective is 86.7%, and Selectivity for paraxylene is 95.3%.
[embodiment 2]
According to condition and the step described in embodiment 1, take methyl alcohol as terminator, terminator temperature is 20 ℃, and Wei Ju gas solid separation district, terminator injection phase bottom level is 1/5 of riser tube height, and raw material and terminator mol ratio are 1000:1, and catalyzer is ZSM-5, SiO
2/ Al
2o
3mol ratio is 500, and loaded metal is 0.5wt%Pd, 8wt%La
2o
3, 5wt%P
2o
5.Reaction conditions is: 600 ℃ of temperature of reaction, reaction pressure is counted 5Mpa with gauge pressure, catalyzer with raw material weight than 20:1, methanol/toluene mol ratio=1:2, water vapour/toluene mole ratio=2:1, does not face hydrogen.Revivifier regeneration temperature is 560 ℃, and the catalyzer of the pre-zone of action of toluene 60% goes revivifier regeneration through inclined tube to be generated by weight, and 40% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 28.1%, and dimethylbenzene selective is 82.4%, and Selectivity for paraxylene is 87.5%.
[embodiment 3]
According to condition and the step described in embodiment 1, take methyl alcohol as terminator, terminator temperature is 25 ℃, and Wei Ju gas solid separation district, terminator injection phase bottom level is 1/5 of riser tube height, and raw material and terminator mol ratio are 30:1, and catalyzer is ZSM-5, SiO
2/ Al
2o
3mol ratio is 100, and loaded metal is 5wt%Pd, 2wt%La
2o
3, 15wt%P
2o
5.Reaction conditions is: 420 ℃ of temperature of reaction, reaction pressure is counted 0.5Mpa with gauge pressure, catalyzer with raw material weight than 0.5, methanol/toluene mol ratio=1:2, CO/ toluene mole ratio=2, do not face hydrogen.Revivifier regeneration temperature is 680 ℃, and the catalyzer of the pre-zone of action of toluene 5% goes revivifier regeneration through inclined tube to be generated by weight, and 95% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 33.9%, and dimethylbenzene selective is 88.6%, and Selectivity for paraxylene is 96.7%.
[embodiment 4]
According to condition and the step described in embodiment 3, take methyl alcohol as terminator, terminator temperature is 300 ℃, Wei Ju gas solid separation district, terminator injection phase bottom level is 1/5 of riser tube height, raw material and terminator mol ratio are 100:1, and catalyzer is SAPO-11, the SiO of SAPO-11 molecular sieve
2/ Al
2o
3mol ratio is 1, P
2o
5/ Al
2o
3mol ratio is 1, SiO
2/ P
2o
5mol ratio is 0.8, and loaded metal is 0.5wt%Pd, 8wt%La
2o
3, 5wt%P
2o
5.Reaction conditions is: 350 ℃ of temperature of reaction, reaction pressure is counted 5Mpa with gauge pressure, catalyzer with raw material weight than 20:1, methanol/toluene mol ratio=1:0.3, hydrogen/toluene mole ratio=8:1.Revivifier regeneration temperature is 680 ℃, and the catalyzer of the pre-zone of action of toluene 20% goes revivifier regeneration through inclined tube to be generated by weight, and 80% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 76.9%, dimethylbenzene selective 74.1%, and Selectivity for paraxylene is 87.2%.
[embodiment 5]
According to condition and the step described in embodiment 3, take methyl alcohol as terminator, terminator temperature is 100 ℃, Wei Ju gas solid separation district, terminator injection phase bottom level is 1/8 of riser tube height, raw material and terminator mol ratio are 100:1, catalyzer is SAPO-11 and ZSM-5, and loaded metal is 0.5wt%Pd, 8wt%La
2o
3, 5wt%P
2o
5.Reaction conditions is: 500 ℃ of temperature of reaction, reaction pressure is counted 1Mpa with gauge pressure, catalyzer with raw material weight than 1:1, methanol/toluene mol ratio=1:10, carrier gas/toluene mole ratio=0:1.Revivifier regeneration temperature is 650 ℃, and the catalyzer of the pre-zone of action of toluene 25% goes revivifier regeneration through inclined tube to be generated by weight, and 75% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 9.2%, and dimethylbenzene selective is 73.2%, and Selectivity for paraxylene is 85.4%.
[embodiment 6]
According to condition and the step described in embodiment 3, take methyl alcohol as terminator, terminator temperature is 60 ℃, Wei Ju gas solid separation district, terminator injection phase bottom level is 1/4 of riser tube height, raw material and terminator mol ratio are 500:1, catalyzer is SAPO-11 and ZSM-5, and the mass ratio of SAPO-11 and ZSM-5 is 1:1, wherein the SiO of ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is the SiO of 100, SAPO-11 molecular sieve
2/ Al
2o
3mol ratio is 2, P
2o
5/ Al
2o
3mol ratio is 1, SiO
2/ P
2o
5mol ratio is 0.5, and loaded metal is 0.3wt%Pd, 30wt%La
2o
3, 10wt%P
2o
5.Reaction conditions is: 500 ℃ of temperature of reaction, reaction pressure is counted 1Mpa with gauge pressure, catalyzer with raw material weight than 1:1, methanol/toluene mol ratio=1:5, carrier gas/toluene mole ratio=0:1.Revivifier regeneration temperature is 650 ℃, and the catalyzer of the pre-zone of action of toluene 25% goes revivifier regeneration through inclined tube to be generated by weight, and 75% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 7.4%, and dimethylbenzene selective is 78.9%, and Selectivity for paraxylene is 83.6%.
[embodiment 7]
According to condition and the step described in embodiment 3, take methyl alcohol as terminator, terminator temperature is 60 ℃, Wei Ju gas solid separation district, terminator injection phase bottom level is 1/4 of riser tube height, raw material and terminator mol ratio are 500:1, catalyzer is SAPO-11 and ZSM-5, and the mass ratio of SAPO-11 and ZSM-5 is 1:1, wherein the SiO of ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is the SiO of 100, SAPO-11 molecular sieve
2/ Al
2o
3mol ratio is 2, P
2o
5/ Al
2o
3mol ratio is 1, SiO
2/ P
2o
5mol ratio is 0.5, and loaded metal is 4wt%Pd, 1wt%La
2o
3.Reaction conditions is: 450 ℃ of temperature of reaction, reaction pressure is counted 1Mpa with gauge pressure, catalyzer with raw material weight than 2:1, methanol/toluene mol ratio=1:5, carrier gas/toluene mole ratio=3:1.Revivifier regeneration temperature is 650 ℃, and the catalyzer of the pre-zone of action of toluene 25% goes revivifier regeneration through inclined tube to be generated by weight, and 75% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 7.9%, and dimethylbenzene selective is 79.4%, and Selectivity for paraxylene is 85.1%.
[embodiment 8]
According to condition and the step described in embodiment 3, take methyl alcohol as terminator, terminator temperature is 60 ℃, Wei Ju gas solid separation district, terminator injection phase bottom level is 1/4 of riser tube height, raw material and terminator mol ratio are 1:1, catalyzer is SAPO-11 and ZSM-5, and the mass ratio of SAPO-11 and ZSM-5 is 1:1, wherein the SiO of ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is the SiO of 200, SAPO-11 molecular sieve
2/ Al
2o
3mol ratio is 2, P
2o
5/ Al
2o
3mol ratio is 1, SiO
2/ P
2o
5mol ratio is 0.5, and loaded metal is 1wt%Pd, 10wt%Ce
2o
3, 3wt%P
2o
5.Reaction conditions is: 450 ℃ of temperature of reaction, reaction pressure is counted 0.1Mpa with gauge pressure, catalyzer with raw material weight than 0.1:1, methanol/toluene mol ratio=1:0.1, carrier gas/toluene mole ratio=3:1.Revivifier regeneration temperature is 650 ℃, and the catalyzer of the pre-zone of action of toluene 60% goes revivifier regeneration through inclined tube to be generated by weight, and 40% returns to reaction zone by catalyzer outer circulating tube after heat exchange.Experimental result is: toluene conversion is 94.5%, and dimethylbenzene selective is 86.4%, and Selectivity for paraxylene is 89.6%.
[comparative example 1]
According to condition and the step described in embodiment 1, just in fast gas-solid separator ingress, do not add terminator, experimental result is: toluene conversion is 27.5%, and dimethylbenzene selective is 82.5%, and Selectivity for paraxylene is 91.2%.
[comparative example 2]
According to condition and the step described in embodiment 2, just in fast gas-solid separator ingress, do not add terminator, experimental result is: toluene conversion is 31.1%, and dimethylbenzene selective is 82.9%, and Selectivity for paraxylene is 88.3%.
[comparative example 3]
Condition and step according to described in embodiment 2, do not add terminator in fast gas-solid separator ingress, and the pre-zone of action of toluene only passes into water vapour as fluidizing medium.Experimental result is: toluene conversion is 25.3%, and dimethylbenzene selective is 81.4%, and Selectivity for paraxylene is 87.1%.
Claims (10)
1. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation, comprises following step:
(1) raw material that comprises methyl alcohol and toluene, through the laggard reaction zone that enters fluidized-bed reactor of heating vaporization, contact with alkylation catalyst, generates the mixture flow that contains p-Xylol;
(2) described mixture flow enters the gas-solid sharp separation district being connected with top, described reaction zone, isolated gas-phase product enters later separation workshop section again after cyclonic separator separation, the isolated catalyzer of gas-solid sharp separation district and cyclonic separator enters the pre-zone of action of toluene, catalyzer at least a portion of the pre-zone of action of toluene enters revivifier regeneration after the stripping of stripping zone, forms regenerated catalyst;
(3) described regenerated catalyst returns to reaction zone and proceeds reaction;
Wherein, in gas-solid sharp separation district, inject terminator, the weight ratio of terminator and raw material is 1:1～1000, and terminator feeding temperature is 20-300 ℃.
2. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that described terminator is selected from least one of methyl alcohol, water.
3. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, the catalyzer that it is characterized in that the pre-zone of action of described toluene 5～60% goes revivifier regeneration through inclined tube to be generated by weight, and 40～95% return to reaction zone by catalyzer outer circulating tube after heat exchange.
4. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, the reaction conditions that it is characterized in that described reaction zone is: temperature of reaction is 350-600 ℃, reaction pressure 0.1-5MPa, toluene and methanol mol ratio 0.1-10:1 in charging, catalyzer compares 0.1-20:1 with raw material weight, in raw material charging, can add carrier gas, carrier gas/toluene mole ratio is 0-8:1.
5. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that described stripping zone stripping medium is water vapour.
6. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that catalyzer continuous flow and regeneration in fluidized-bed reactor and revivifier, in revivifier, contacted burning-off carbon distribution by air with catalyzer, revivifier regeneration temperature is 560 ℃-680 ℃.
7. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that described alkylation catalyst comprises at least one in molecular sieve and hydrogenation metal or its oxide compound, rare earth metal or its oxide compound, nonmetal oxide; At least one in ZSM-5, ZSM-11, ZSM-22, ZSM-23, FMI, MCM-22, MCM-56, MCM-49, SAPO-11, EU-1 of molecular screening; Hydrogenation metal is selected from least one in platinum, palladium, nickel, molybdenum, copper, zinc, cobalt; Rare earth metal is selected from lanthanum or cerium; Nonmetal at least one being selected from boron, nitrogen or phosphorus.
8. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 7, it is characterized in that the molecular sieve in described alkylation catalyst is ZSM-5, SiO
2/ Al
2o
3mol ratio is 100-500; Hydrogenation metal is platinum, palladium, nickel, molybdenum, cobalt; Nonmetal is boron or phosphorus; Component in described alkylation catalyst is counted with parts by weight: a) 50-80 part ZSM-5 molecular sieve; B) 0.3-4 part hydrogenation metal or oxide compound; C) 1-30 part rare earth metal or its oxide compound; D) 0-10 part nonmetal oxide.
9. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that passing in the pre-zone of action of described toluene comprise toluene logistics as fluidizing medium.
10. methylbenzene methanol is selected the bed process that p-Xylol is produced in type alkylation according to claim 4, it is characterized in that described carrier gas is water vapour, H
2, at least one in CO.
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