CN103588601B - Methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation - Google Patents
Methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation Download PDFInfo
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Abstract
The present invention relates to a kind of methylbenzene methanol and select the bed process that p-Xylol is produced in type alkylation, mainly solve the problem that in prior art, Selectivity for paraxylene is lower.The bed process of the present invention by adopting a kind of methylbenzene methanol to select type alkylation production p-Xylol, comprise following step: (1) raw material through heat laggard enter the reaction zone of fluidized-bed reactor, contact with alkylation catalyst, generate the mixture flow containing p-Xylol; (2) mixture flow enters and gas-solid sharp separation district, isolated gas-phase product enters later separation workshop section, isolated catalyzer enters toluene pre-terminated contact area, and the catalyzer of toluene pre-terminated contact area enters revivifier regeneration at least partially after the stripping of stripping zone, forms regenerated catalyst; (3) described regenerated catalyst return reaction zone proceed react technical scheme solve the problems referred to above preferably, can be used in the production of p-Xylol.
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 synthesis terephthalic acid and the main raw material of dimethyl terephthalate (DMT), the demand of dimethylbenzene particularly p-Xylol constantly increases.At present, the technique of domestic and international industrial production p-Xylol mainly comprises toluene disproportionation, accordance transfer, MTA technique etc., all there is the problems such as raw material availability is low, dimethylbenzene selective is poor.Adopt toluene-methanol to select type alkylation p-Xylol technique, low yield benzene does not even produce benzene, meets the present situation of domestic benzene glut the market, effectively improves 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.But the alkylating reagent methyl alcohol very easily coking at reaction conditions of introducing, causes catalyst deactivation, Selectivity for paraxylene is deteriorated, and solves the key that deactivation prob is alkylation of toluene methanol technical development always.
Adopt fluidized-bed reactor can carry out regenerated in real time to decaying catalyst, decrease side reaction adding of terminator simultaneously, efficiently solve fixed bed reactor catalyst inactivation fast, the problem that Selectivity for paraxylene is low.Alkylating reagent containing methyl alcohol, dme divides multiply to introduce reactor from one or more positions in fluidized-bed reactor entrance downstream by patent CN102372585, this can make alkylating reagent be uniformly distributed in reactor on the one hand, effectively promotes use ratio of methanol.But the ununiformity that alkylating reagent mixes with aromatic hydrocarbons adds the possibility that himself reacts.Patent CN101417236 discloses a kind of fluid catalyst of alkylation p-Xylol coproduction 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 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%.
Technical problem underlying involved in above-mentioned document is that particularly alkylating reagent methyl alcohol is long for duration of contact with catalyst ineffective for reactant, is not separated in time or stopped reaction, causes side reaction particularly coking reaction increase, catalyzer easy in inactivation.Simultaneous reactions air speed is lower, and the selectivity of object product is lower.
The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, Selectivity for paraxylene is lower, provides a kind of new methylbenzene methanol to select the bed process of type alkylation production p-Xylol.The method is used for, in the production of p-Xylol, having the advantage that Selectivity for paraxylene is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation, comprise following step: the raw material that (1) comprises methyl alcohol and toluene through heat vaporized laggard enter the reaction zone of fluidized-bed reactor, contact with alkylation catalyst, generate the mixture flow containing p-Xylol; (2) described mixture flow enters the gas-solid sharp separation district be connected with top, described reaction zone, isolated gas-phase product enters later separation workshop section again after cyclonic separator is separated, gas-solid sharp separation district and the isolated catalyzer of cyclonic separator enter toluene pre-terminated contact area, the catalyzer of toluene pre-terminated contact area enters revivifier regeneration at least partially 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 DEG C.
In technique scheme, preferably, described terminator is selected from least one of methyl alcohol, water.
In technique scheme, preferably, the catalyzer of described toluene pre-terminated contact area 5 ~ 60% goes revivifier to regenerate through inclined tube to be generated by weight, and 40 ~ 95% return to reaction zone by external catalyst circulation pipe after heat exchange.
In technique scheme, preferably, the reaction conditions of described reaction zone is: temperature of reaction is 350-600 DEG C, reaction pressure 0.1-5MPa, toluene and methanol mol ratio 0.1-10:1 in charging, catalyzer and raw material weight, than 0.1-20:1, can add carrier gas in feedstock, 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 fluid is water vapour.
In technique scheme, preferably, catalyzer is continuous flow and regeneration in fluidized-bed reactor and revivifier, and by air and catalyst exposure burning-off carbon distribution in revivifier, revivifier regeneration temperature is 560 DEG C-680 DEG C.
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 of molecular screening in ZSM-5, ZSM-11, ZSM-22, ZSM-23, FMI, MCM-22, MCM-56, MCM-49, SAPO-11, EU-1; Hydrogenation metal is selected from least one in platinum, palladium, nickel, molybdenum, copper, zinc, cobalt; Rare earth metal is selected from lanthanum or cerium; The nonmetal at least one be 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, pass in described toluene pre-terminated contact area comprise toluene logistics as fluidizing medium.
The following formula of reaction parameter in the present invention obtains:
Terminator described in the present invention is selected from least one in methyl alcohol, ethanol, water.
Prepare in p-Xylol technique at alkylation of toluene methanol, easily coking reaction is there is in alkylating reagent methyl alcohol under contacting with long-lasting catalytic, cause catalyst deactivation, circulating fluid bed reactor is adopted to make catalyzer can regenerated in real time, the distribution of simultaneous reactions bed temperature is more even, heat of reaction is effectively spread, and substantially increases catalytic efficiency and solves catalyzer easy in inactivation problem.But in the negative area of fluidized-bed reactor, a large amount of unsegregated catalyzer at high temperature can continue and product generation secondary reaction, makes side reaction increase, and causes object product Selectivity for paraxylene to reduce.The present invention injects the low temperature terminator of water or methyl alcohol at gas-solid separator entrance, does not introduce other material in reaction system, significantly reduces the temperature of catalyzer and reaction mixture, reactor temperature rise is reduced.And temperature is the key controlling reaction, maintains stable temperature and both ensured carrying out smoothly of alkylation main reaction, make again side reaction reduce, effectively improve the selectivity of object product.Simultaneously, catalyzer after gas solid separation enters toluene pre-terminated contact area, toluene is fully adsorbed in the duct of catalyzer, when contacting alkylating reagent methyl alcohol, can highly selective, be converted into p-Xylol fast, meet the short requirement need accelerating rate of mass transfer duration of contact of fluidized-bed reactor agent material.Adopt fluidized-bed reactor of the present invention in alkylation of toluene methanol p-Xylol technique, be 350-600 DEG C in temperature of reaction, reaction pressure 0.1-5MPa, fed toluene/methanol molar ratio 0.1-10:1, catalyzer and raw material weight are 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%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the reaction-regeneration system schematic flow sheet of the method for the invention.
1 is methanol toluene feedstock and carrier gas; 2 is external catalyst circulation pipe; 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 product gas outlet; 11 is stripping zone; 12 is water stripping vapor feed pipeline; 13 is toluene feed line; 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 toluene pre-terminated contact area; 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 DEG C, terminator injection phase is distance gas solid separation district 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, enter bottom fluidized-bed reactor after heat exchange preheating, contact with alkylation catalyst in reaction zone, generate the mixture being rich in p-Xylol, reaction conditions is: temperature of reaction 420 DEG C, and reaction pressure counts 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 DEG C, toluene pre-terminated contact area passes into toluene as fluidizing medium, toluene pre-terminated contact area linear speed is 0.15m/s, and the catalyzer of toluene pre-terminated contact area 50% goes revivifier to regenerate through inclined tube to be generated by weight, and 50% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 1 and step, take methyl alcohol as terminator, terminator temperature is 20 DEG C, and terminator injection phase is distance gas solid separation district 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: temperature of reaction 600 DEG C, and reaction pressure counts 5Mpa with gauge pressure, and catalyzer and raw material weight are than 20:1, and methanol/toluene mol ratio=1:2, water vapour/toluene mole ratio=2:1, does not face hydrogen.Revivifier regeneration temperature is 560 DEG C, and the catalyzer of toluene pre-terminated contact area 60% goes revivifier to regenerate through inclined tube to be generated by weight, and 40% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 1 and step, take methyl alcohol as terminator, terminator temperature is 25 DEG C, and terminator injection phase is distance gas solid separation district 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: temperature of reaction 420 DEG C, and reaction pressure counts 0.5Mpa with gauge pressure, and catalyzer and raw material weight are than 0.5, and methanol/toluene mol ratio=1:2, CO/ toluene mole ratio=2, do not face hydrogen.Revivifier regeneration temperature is 680 DEG C, and the catalyzer of toluene pre-terminated contact area 5% goes revivifier to regenerate through inclined tube to be generated by weight, and 95% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 3 and step, take methyl alcohol as terminator, terminator temperature is 300 DEG C, terminator injection phase is distance gas solid separation district bottom level is 1/5 of riser tube height, raw material and terminator mol ratio are 100:1, and catalyzer is the SiO of SAPO-11, 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: temperature of reaction 350 DEG C, and reaction pressure counts 5Mpa with gauge pressure, catalyzer and raw material weight than 20:1, methanol/toluene mol ratio=1:0.3, hydrogen/toluene mole ratio=8:1.Revivifier regeneration temperature is 680 DEG C, and the catalyzer of toluene pre-terminated contact area 20% goes revivifier to regenerate through inclined tube to be generated by weight, and 80% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 3 and step, take methyl alcohol as terminator, terminator temperature is 100 DEG C, terminator injection phase is distance gas solid separation district 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: temperature of reaction 500 DEG C, and reaction pressure counts 1Mpa with gauge pressure, catalyzer and raw material weight than 1:1, methanol/toluene mol ratio=1:10, carrier gas/toluene mole ratio=0:1.Revivifier regeneration temperature is 650 DEG C, and the catalyzer of toluene pre-terminated contact area 25% goes revivifier to regenerate through inclined tube to be generated by weight, and 75% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 3 and step, take methyl alcohol as terminator, terminator temperature is 60 DEG C, terminator injection phase is distance gas solid separation district bottom level is 1/4 of riser tube height, raw material and terminator mol ratio are 500:1, catalyzer is the mass ratio of SAPO-11 and ZSM-5, SAPO-11 and ZSM-5 is 1:1, the wherein 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: temperature of reaction 500 DEG C, and reaction pressure counts 1Mpa with gauge pressure, catalyzer and raw material weight than 1:1, methanol/toluene mol ratio=1:5, carrier gas/toluene mole ratio=0:1.Revivifier regeneration temperature is 650 DEG C, and the catalyzer of toluene pre-terminated contact area 25% goes revivifier to regenerate through inclined tube to be generated by weight, and 75% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 3 and step, take methyl alcohol as terminator, terminator temperature is 60 DEG C, terminator injection phase is distance gas solid separation district bottom level is 1/4 of riser tube height, raw material and terminator mol ratio are 500:1, catalyzer is the mass ratio of SAPO-11 and ZSM-5, SAPO-11 and ZSM-5 is 1:1, the wherein 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: temperature of reaction 450 DEG C, and reaction pressure counts 1Mpa with gauge pressure, catalyzer and raw material weight than 2:1, methanol/toluene mol ratio=1:5, carrier gas/toluene mole ratio=3:1.Revivifier regeneration temperature is 650 DEG C, and the catalyzer of toluene pre-terminated contact area 25% goes revivifier to regenerate through inclined tube to be generated by weight, and 75% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 3 and step, take methyl alcohol as terminator, terminator temperature is 60 DEG C, terminator injection phase is distance gas solid separation district bottom level is 1/4 of riser tube height, raw material and terminator mol ratio are 1:1, catalyzer is the mass ratio of SAPO-11 and ZSM-5, SAPO-11 and ZSM-5 is 1:1, the wherein 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: temperature of reaction 450 DEG C, and reaction pressure counts 0.1Mpa with gauge pressure, catalyzer and 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 DEG C, and the catalyzer of toluene pre-terminated contact area 60% goes revivifier to regenerate through inclined tube to be generated by weight, and 40% returns to reaction zone by external catalyst circulation pipe 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 the condition described in embodiment 1 and step, just do not add terminator in fast gas-solid separator ingress, 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 the condition described in embodiment 2 and step, just do not add terminator in fast gas-solid separator ingress, experimental result is: toluene conversion is 31.1%, and dimethylbenzene selective is 82.9%, and Selectivity for paraxylene is 88.3%.
[comparative example 3]
According to the condition described in embodiment 2 and step, do not add terminator in fast gas-solid separator ingress, toluene pre-terminated contact area 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 (9)
1. methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation, comprises following step:
(1) raw material comprising methyl alcohol and toluene through heat vaporized laggard enter the reaction zone of fluidized-bed reactor, contact with alkylation catalyst, generate the mixture flow containing p-Xylol;
(2) described mixture flow enters the gas-solid sharp separation district be connected with top, described reaction zone, isolated gas-phase product enters later separation workshop section again after cyclonic separator is separated, gas-solid sharp separation district and the isolated catalyzer of cyclonic separator enter toluene pre-terminated contact area, the catalyzer of toluene pre-terminated contact area enters revivifier regeneration at least partially 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 DEG C; Described terminator is selected from water.
2. methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that the catalyzer of described toluene pre-terminated contact area 5 ~ 60% goes revivifier to regenerate through inclined tube to be generated by weight, 40 ~ 95% return to reaction zone by external catalyst circulation pipe after heat exchange.
3. methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that the reaction conditions of described reaction zone is: temperature of reaction is 350-600 DEG C, 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, can add carrier gas in feedstock, carrier gas/toluene mole ratio is 0-8:1.
4. methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation according to claim 1, it is characterized in that described stripping zone stripping fluid is water vapour.
5. methylbenzene methanol selects 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, by air and catalyst exposure burning-off carbon distribution in revivifier, revivifier regeneration temperature is 560 DEG C-680 DEG C.
6. methylbenzene methanol is selected type alkylation and is produced the bed process of p-Xylol 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 of molecular screening in ZSM-5, ZSM-11, ZSM-22, ZSM-23, FMI, MCM-22, MCM-56, MCM-49, SAPO-11, EU-1; Hydrogenation metal is selected from least one in platinum, palladium, nickel, molybdenum, copper, zinc, cobalt; Rare earth metal is selected from lanthanum or cerium; The nonmetal at least one be selected from boron, nitrogen or phosphorus.
7. methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation according to claim 6, 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.
8. methylbenzene methanol is selected type alkylation and is produced the bed process of p-Xylol according to claim 1, it is characterized in that passing in described toluene pre-terminated contact area comprise toluene logistics as fluidizing medium.
9. methylbenzene methanol selects the bed process that p-Xylol is produced in type alkylation according to claim 3, it is characterized in that described carrier gas is water vapour, H
2, at least one in CO.
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| BR112019006912A2 (en) * | 2016-10-06 | 2019-07-02 | Exxonmobil Chemical Patents Inc | process for producing paraxylene by methylation of benzene and / or toluene |
| CN106854128B (en) * | 2016-11-28 | 2019-11-22 | 陕西煤化工技术工程中心有限公司 | A kind of method that toluene produces paraxylene with methanol |
| CN106807442A (en) * | 2017-01-16 | 2017-06-09 | 惠生工程（中国）有限公司 | A kind of shape-selective catalyst with toluene methylation efficiency high and its preparation method and application |
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| CN108786670B (en) * | 2017-04-27 | 2021-01-26 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing low-carbon olefin by methanol and/or dimethyl ether and toluene |
| CN108786671B (en) * | 2017-04-27 | 2021-04-23 | 中国科学院大连化学物理研究所 | Fluidized bed device and method for preparing p-xylene and co-producing low-carbon olefin by methanol and/or dimethyl ether and benzene |
| CN108794291B (en) | 2017-04-27 | 2020-11-27 | 中国科学院大连化学物理研究所 | Fluidized bed device and method for preparing p-xylene and co-producing low-carbon olefin by methanol and/or dimethyl ether and toluene |
| CN108786672B (en) | 2017-04-27 | 2021-01-26 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing low-carbon olefin by using methanol and/or dimethyl ether and benzene |
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|---|---|---|---|---|
| CN102372585B (en) * | 2010-08-23 | 2015-12-09 | 中国石油化工股份有限公司 | The bed process of alkylating aromatic hydrocarbon p-Xylol |
| CN102372584B (en) * | 2010-08-23 | 2014-07-23 | 中国石油化工股份有限公司 | Fluidized catalytic method for preparing p-xylene by alkylating aromatic hydrocarbon |
| CN102464557B (en) * | 2010-11-17 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing dimethylbenzene from oxygen-containing compound and methylbenzene |
| CN102463085B (en) * | 2010-11-17 | 2014-01-22 | 中国石油化工股份有限公司 | Reaction device for producing dimethylbenzene from methanol or dimethyl ether and methylbenzene |
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