CN107586246A - The method that aromatisation produces aromatic hydrocarbon - Google Patents
The method that aromatisation produces aromatic hydrocarbon Download PDFInfo
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- CN107586246A CN107586246A CN201610539618.4A CN201610539618A CN107586246A CN 107586246 A CN107586246 A CN 107586246A CN 201610539618 A CN201610539618 A CN 201610539618A CN 107586246 A CN107586246 A CN 107586246A
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Abstract
The present invention relates to a kind of method of aromatisation production aromatic hydrocarbon, including in the presence of water, raw material and catalyst contacted under the conditions of aromatization and the step of manufacture aromatic hydrocarbon；Wherein, the raw material has structure formula (I)：In formula (I), R1And R2The C for hydrogen, optionally substituted1‑20Straight or branched alkyl, the C optionally substituted2‑20Straight or branched alkenyl, the C optionally substituted2‑20Straight or branched alkynyl, the C optionally substituted3‑20Cycloalkyl or the C optionally substituted6‑20Aryl.
Description
Technical field
The present invention relates to a kind of method of aromatisation production aromatic hydrocarbon, particularly a kind of method of manufacture BTX aromatic hydrocarbon.This
The method that invention manufactures paraxylene and terephthalic acid (TPA) further to the manufacture method based on the aromatic hydrocarbon.
Background technology
Aromatic hydrocarbon product is widely used in the numerous areas such as polyester, chemical fibre, rubber, medicine and fine chemistry industry, domestic consumption
Measure considerable, there is material impact to the national economic development, while be the important basic organic chemical industry raw material of social development.Benzene, first
Benzene, dimethylbenzene are widely used three kinds of aromatic hydrocarbons bulk chemicals in aromatic hydrocarbons, are referred to as lightweight aromatic hydrocarbon or BTX aromatic hydrocarbon.Benzene
It is a kind of basic petrochemical material of multipurpose, its derivative numerous product, including ethyl benzene/styrene, cumene/phenol can be produced
Etc..Paraxylene passes through terephthalic acid (TPA) (PTA) or diethyl terephthalate mainly for the manufacture of terephthalic acid (TPA)
(DMT) intermediate, for producing poly- cruel fiber such as polyethylene terephthalate (PET), resin and film.At present both at home and abroad
The production of aromatic hydrocarbons depends on non-renewable fossil resource, such as by a catalyst by oil by hydrogenation, reform,
The technical process such as aromatic hydrocarbons conversion and separation obtains.But because fossil resource reserves finite sum is non-renewable so that with oil
More see for the main cost for refining raw material production aromatic hydrocarbons surging.In addition, the utilization of continually developing of fossil resource produces a large amount of greenhouses
Gas discharges, and caused a series of environmental problems is on the rise.Therefore, develop (outstanding from renewable resource route production aromatic hydrocarbons
It is BTX aromatic hydrocarbon) technology it is significant.
As renewable resource, using biological material as raw material come manufacture aromatic hydrocarbon be current technology study hotspot it
One.Prior art is present the report that conversion of biomass material is aromatic hydrocarbon, also discloses that and a variety of uses flat for this purpose
Platform compound (such as referring to Katherine Bourzac, From biomass to chemicals in one step, MIT
Technology Review,2010-03-29；CN104230615A；US20090227823 and US20110257416A1).
Tetrahydrofurans are widely used, typical case such as methyltetrahydrofuran (2-MeTHF) and tetrahydrofuran (THF).
A kind of conventional middle polarity non-protonic solvents of wherein THF.Its precursor for being mainly used for making high molecular polymer, strong
It polymerize catenulate PolyTHF in sour environment, for manufacturing elastic polyurethane fiber, such as spandex (^Polyethers,
Tetrahydrofuran and Oxetane Polymers by Gerfried Pruckmayr,P.Dreyfuss,
M.P.Dreyfuss//Kirk-Othmer Encyclopedia of Chemical Technology.John Wiley&
Sons,Inc.1996.)；Industrial solvent (Herbert M ü ller, " can also be made in the production of PVC and paint
Tetrahydrofuran"in Ullmann's Encyclopedia of Industrial Chemistry 2002,Wiley-
VCH,Weinheim.)。
Present inventor is that platform chemicals aromatisation prepares BTX aromatic hydrocarbons patent applied fors with regard to tetrahydrofurans
(CN201510345862.2).But found in follow-up R＆D process, tetrahydrofurans are deposited in conversion process
In C4 alkene intermediates, easily form polyolefin and carbon distribution, coking cause catalyst inactivation and service life on catalyst
It is short；Simultaneously as aromatized catalyst inactivates, its aromatizing capacity also drastically declines, and causes arenes selectivity in final product
Decline.In order to maintain the aromatizing capacity of catalyst, catalyst needs frequent regeneration.
The content of the invention
The technical problems to be solved by the invention are that alkene is unavoidably produced in tetrahydrofurans aromatization process
Hydrocarbon species, so as to generate carbon distribution, a kind of the problem of causing catalyst inactivation, there is provided side of new aromatisation production aromatic hydrocarbon
Method.This method can effectively remove carbon distribution, recover the aromatization activity of catalyst, so as to extend the service life of catalyst.
In order to solve the above technical problems, the technical scheme that the present invention takes is as follows：A kind of side of aromatisation production aromatic hydrocarbon
Method, including in the presence of water, the step of raw material manufactures aromatic hydrocarbon with catalyst being contacted under the conditions of aromatization；Wherein,
The raw material has structure formula (I)：
In formula (I), R1And R2The C for hydrogen, optionally substituted1-20Straight or branched alkyl, the C optionally substituted2-20Straight chain or branch
Alkenyl, the C optionally substituted2-20Straight or branched alkynyl, the C optionally substituted3-20Cycloalkyl or the C optionally substituted6-20Virtue
Base.
In above-mentioned technical proposal, in formula (I), R1And R2Preferably hydrogen, the C optionally substituted2-10Straight or branched alkyl, appoint
Choose the C in generation2-10Straight or branched alkenyl.
In above-mentioned technical proposal, the dosage of the water is：The mass fraction of water accounts for water and has the raw material of structure formula (I)
The 0.01~99.99% of gross mass, preferably 1~90%, more preferably 10~60%.
In above-mentioned technical proposal, the catalyst is molecular sieve, and the molecular sieve is selected from ZSM types molecular sieve, Y type molecules
At least one of sieve, Beta types molecular sieve, L-type molecular sieve or MCM type molecular sieves.
In above-mentioned technical proposal, the molecular sieve is preferably combination of molecular sieve, and in terms of parts by weight, it is included with the following group
Part：
A) 20~80 parts of the molecular sieve；
B) 20~80 parts of binding agent.
In above-mentioned technical proposal, the molecular sieve is selected from ZSM-5, ZSM-11, ZSM-23, ZSM-38, Y, Beta, MCM-22
Or at least one of MCM-41 molecular sieves；Preferably at least one of ZSM-5, Y, Beta or MCM-41 molecular sieve.
In above-mentioned technical proposal, the silica alumina ratio SiO of the ZSM types molecular sieve2/Al2O3=10~500；Preferably
SiO2/Al2O3=15~100.
In above-mentioned technical proposal, the silica alumina ratio SiO of Y type molecular sieve2/Al2O3=2~70；Preferably SiO2/Al2O3
=3~50.
In above-mentioned technical proposal, the silica alumina ratio SiO of Beta type molecular sieves2/Al2O3=10~150；Preferably SiO2/
Al2O3=15~65.
In above-mentioned technical proposal, the silica alumina ratio SiO of MCM type molecular sieves2/Al2O3=20~250；Preferably SiO2/
Al2O3=40~150.
In above-mentioned technical proposal, the silica alumina ratio SiO of L-type molecular sieve2/Al2O3=5~100, preferably SiO2/Al2O3
=6~35.
In above-mentioned technical proposal, the binding agent be selected from Ludox, boehmite, aluminum oxide, kaolin, montmorillonite or
At least one of bentonite.
In above-mentioned technical proposal, the aromatization condition includes：300~800 DEG C of reaction temperature, preferably 300~650
℃；Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, preferably 0.5~4MPa；Raw material weight air speed 0.3~10 hour-1；It is preferred that 0.5~
5 hours-1。
In above-mentioned technical proposal, the raw material biomass derived material.As the biological material, for example can lift
Go out this area conventionally used for aromatic hydrocarbon manufacture purposes those, specifically can such as enumerate xylitol, glucose, cellobiose,
Cellulose, hemicellulose and lignin etc..These biological materials can be used alone, can also combination of two or more make
With.
In above-mentioned technical proposal, as the biological material, paper mill sludge, waste paper, sweet specifically can also be such as enumerated
Bagasse, glucose, timber, corncob, corn stalk and rice straw etc..These biological materials can be used alone, can also
Combination of two or more uses.Here, by weight percentage, content of cellulose is usually 30- in the biological material
99%, hemicellulose level is usually 0-50%, and content of lignin is usually 0 or 1-40%.
In above-mentioned technical proposal, in addition to biological material is set to carry out catalyzed conversion, the step of obtaining the raw material.
Combination of molecular sieve described in the inventive method can be directly using commercially available prod or according to known in the art
Method manufactured.Specifically, the manufacture method as the combination of molecular sieve, for example following methods can be enumerated：
By molecular sieve, binding agent and the extrusion aid used as needed, expanding agent and water kneading resulting mixture, extruded moulding, Ran Hou
100~200 DEG C of dryings 1~24 hour, are calcined 1~10 hour at 400~700 DEG C.As the extrusion aid, such as can be with
Enumerate those commonly used in the art such as sesbania powder, polyethylene glycol or sodium carboxymethylcellulose；And the expanding agent is used as, than
As can enumerate citric acid, oxalic acid or ethylenediamine tetra-acetic acid etc. it is commonly used in the art.In general, extrusion aid and expansion
The addition total amount of hole agent is no more than the 10wt% of the gross weight of the mixture.As needed, acid can also be added during shaping.Make
For the acid, for example inorganic acid, acetic acid or its aqueous solution etc., the particularly aqueous solution of nitric acid, sulfuric acid or phosphoric acid can be enumerated.One
As for, the addition of the sour aqueous solution accounts for 50~90wt% of the gross weight of the mixture.
As an embodiment of the invention, the tetrahydrofurans come from biological material.Such as 2- first
Base tetrahydrofuran, 2- methyltetrahydrofurans can be obtained in hydrogenation cyclisation after hydrolyzing and levulic acid is made by cellulose
(Efficient Conversion of Cellulose to Levulinic Acid by Hydrothermal
Treatment Using Zirconium Dioxide as a Recyclable Solid Acid Catalyst,
Ind.Eng.Chem.Res.,2014,53(49),pp 18796–18805；Production of levulinic acid
from cellulose by hydrothermal decomposition combined with aqueous phase
Dehydration with a solid acid catalyst, Energy Environ.Sci., 2012,5,7559-7574；
Direct Hydrocyclization of Biomass-Derived Levulinic Acid to 2-
Methyltetrahydrofuran over Nanocomposite Copper/Silica ChemSusChem, 2011,4:
1749–1752.).It can also be obtained after hydrolyzing and gamma-valerolactone is made after repeated hydrogenation.(gamma-valerolactone prepares Direct
conversion of cellulose to levulinic acid and gamma-valerolactone using solid
Acid catalysts, Catal.Sci.Technol., 2013,3,927-931；Production of levulinic acid
and gamma-valerolactone(GVL)from cellulose using GVL as a solvent in biphasic
Systems, Energy Environ.Sci., 2012,5,8199-8203；Repeated hydrogenation is four
Hydrogen furans Solvent-free γ-valerolactone hydrogenation to 2-
Methyltetrahydrofuran catalysed by Ru/C, Green Chem., 2014,16,1358-1364).
Contact procedure described in the inventive method can be carried out in one or more reactors.As the reactor,
For example hearth reactor can be enumerated, particularly fixed bed reactors, fluidized-bed reactor, fluidized bed reactor or its combination.
Now, the mode of operation of the reactor both can be the mode of interval or continuous mode, not limit particularly
It is fixed.
Aromatic hydrocarbon is produced as product according to foregoing aromatization method.In general, in the aromatic product,
By weight percentage, the content of BTX aromatic hydrocarbon accounts for more than the 60% of gross weight, and especially, benzene content is 5.0~10.0%,
Toluene level is 30.0~40.0%, and xylene content is 28.0~40.0%, and remaining is non-aromatic hydrocarbon and weight aromatic hydrocarbon.It is described
Weight aromatic hydrocarbon refers to carbon nine and its aromatic hydrocarbon of the above.
After aromatic hydrocarbon is produced as product according to the foregoing aromatization method of the present invention, pass through separation, you can from
Paraxylene is isolated in the aromatic product.In consideration of it, the invention further relates to a kind of manufacture method of paraxylene, it includes
The step of aromatic hydrocarbon being manufactured according to the aromatization method of the present invention；The step of with paraxylene is isolated from the aromatic hydrocarbon.
It is not special to method that paraxylene is isolated from the aromatic hydrocarbon as an embodiment of the invention
Restriction, can directly be applicable those conventionally known in this area.
As an embodiment of the invention, can be manufactured pair using the paraxylene of the foregoing manufacture of the present invention as raw material
Phthalic acid.In consideration of it, the invention further relates to a kind of manufacture method of terephthalic acid (TPA), it is included according to foregoing pair of the present invention
The step of manufacture method manufacture paraxylene of dimethylbenzene；The step of with paraxylene is converted into terephthalic acid (TPA).
It is not special to method that paraxylene is converted into terephthalic acid (TPA) as an embodiment of the invention
Limit, can directly be applicable those conventionally known in this area.
To describe the result of the present invention, in the context of the present specification, using T60 as evaluation index.T60 indexs are
Refer to, as reaction is carried out, the selectivity of BTX aromatic hydrocarbons is reduced to for 60% reaction time in end-product.For example, work as T60=10,
Illustrate reaction after 10 hours, the selectivity of BTX aromatic hydrocarbons drops to 60% in product；As T60=1000, show to react
After 1000 hours, the selectivity of BTX aromatic hydrocarbons drops to 60% in product.Index T60 numerical value is bigger, shows catalyst
Anti-carbon performance is better, and usage time is longer.
The inventive method has preferable effect to the service life for extending aromatized catalyst, solves biomass aromatic hydrocarbons
During aromatized catalyst easy in inactivation, the problem of needing frequent regeneration.Using the inventive method, make the original with structure formula (I)
The aromatization of material is carried out in presence of water, and using under aromatization conditions, the carbon distribution in water and catalyst reacts
CO is formed, so as to remove carbon distribution, recovers the aromatization activity of catalyst, and then extends the service life of catalyst, reduces regeneration
The frequency, feed stock conversion can reach 99%, and the T60 of aromatic hydrocarbons achieved preferable technique effect up to 1356 hours.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Comparative example】
100 grams of corn stalks are weighed, is placed in autoclave pressure and adds 700 grams of water, add the 5mol/L of water quality 7% sulphur
Acid solution, it is warming up at 180 DEG C and reacts 45 minutes, cool down afterwards, by the reacting liquid filtering after cooling, obtain filter cake and filtering
Liquid, filtered fluid are the hydrolyzate of cellulose, after reaction terminates, use mass spectrum to carry out identifying primary product for acetyl to reaction result
Propionic acid, its yield are 34 grams.Obtained levulic acid is in fixed bed reactors Cu/SiO2250 DEG C of 3MPa pressure on catalyst
Under, air speed 0.6h-1Under the conditions of hydrogenation obtain 2- methyltetrahydrofurans, yield 91%.
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 25 to be mixed with 35 grams of gama-aluminas, add 2.7 grams of sesbania powder, mixing
Uniformly.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Obtain catalyst
Precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C1.
Catalyst activity evaluation is carried out on a fixed bed, reaction condition：Catalyst quality is 3 grams, and reaction substrate is 2- first
Base tetrahydrofuran, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.Reaction terminates
Afterwards, the selectivity that 2- methyltetrahydrofurans conversion ratio is 93%, BTX is that 85%, T60 is 85 hours.
【Embodiment 1】
100 grams of corn stalks are weighed, is placed in autoclave pressure and adds 700 grams of water, add the 5mol/L of water quality 7% sulphur
Acid solution, it is warming up at 180 DEG C and reacts 45 minutes, cool down afterwards, by the reacting liquid filtering after cooling, obtain filter cake and filtering
Liquid, filtered fluid are the hydrolyzate of cellulose, after reaction terminates, use mass spectrum to carry out identifying primary product for acetyl to reaction result
Propionic acid, its yield are 34 grams.Obtained levulic acid is in fixed bed reactors Cu/SiO2250 DEG C of 3MPa pressure on catalyst
Under, air speed 0.6h-1Under the conditions of hydrogenation obtain 2- methyltetrahydrofurans, yield 91%.
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 25 to be mixed with 35 grams of gama-aluminas, add 2.7 grams of sesbania powder, mixing
Uniformly.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Obtain catalyst
Precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C1.
Catalyst activity evaluation is carried out on a fixed bed, reaction condition：Catalyst quality is 3 grams, and reaction substrate is 2- first
Base tetrahydrofuran+water (60：40), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature 450
℃.After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 92%, T60 is 1073 hours.
【Embodiment 2】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 50 to be mixed with 35 grams of boehmites, add 2.7 grams of sesbania powder, mix
Close uniform.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C2.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is tetrahydrochysene furan
Mutter+water (30：70), weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction knot
Shu Hou, tetrahydrofuran conversion ratio are that 95%, T60 is 1189 hours.
【Embodiment 3】
60 grams of corn stalks are weighed, is placed in autoclave pressure and adds 700 grams of water, add the 5mol/L of water quality 7% sulphur
Acid solution, it is warming up at 180 DEG C and reacts 45 minutes, cool down afterwards, by the reacting liquid filtering after cooling, obtain filter cake and filtering
Liquid, filtered fluid are the hydrolyzate of cellulose, after reaction terminates, use mass spectrum to carry out identifying primary product for acetyl to reaction result
Propionic acid, its yield are 18 grams.Obtained levulic acid is in fixed bed in the Cu/SiO of 20% content of metal2Upper 220 DEG C
Hydrogenation obtains 2- methyltetrahydrofurans, conversion ratio 99%, product yield 93% under 3MPa pressure.
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 150 to be mixed with 35 grams of boehmites, add 2.7 grams of sesbania powder, mix
Close uniform.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C3.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (60：40), weight space velocity 0.4 hour-1, Hydrogen Vapor Pressure 3.0MPa, flow 50ml min-1, 500 DEG C of temperature.
After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 99%, T60 is 1356 hours.
【Embodiment 4】
Weigh the ZSM-5 that 80 grams of silica alumina ratios are 500 to be mixed with 20 grams of boehmites, add 3.9 grams of sesbania powder, mix
Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C4.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is tetrahydrochysene furan
Mutter+water (20：80), weight space velocity 5.0 hours-1, Hydrogen Vapor Pressure 2.0MPa, flow 30ml min-1, 380 DEG C of temperature.Reaction knot
Shu Hou, tetrahydrofuran conversion ratio are that 96%, T60 is 940 hours.
【Embodiment 5】
Weigh the ZSM-38 that 80 grams of silica alumina ratios are 150 to be mixed with 20 grams of Ludox, add 3.9 grams of sesbania powder, mixing
Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C5.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (99：1), weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 480 DEG C of temperature.Instead
After should terminating, 2- methyltetrahydrofurans conversion ratio is that 95%, T60 is 1060 hours.
【Embodiment 6】
Weigh the ZSM-11 that 80 grams of silica alumina ratios are 150 to be mixed with 20 grams of Ludox, add sodium carboxymethylcellulose 3.9
Gram, it is well mixed.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.
Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C6.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (90：10), weight space velocity 1.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 420 DEG C of temperature.
After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 95%, T60 is 1320 hours.
【Embodiment 7】
Weigh the ZSM-11 that 70 grams of silica alumina ratios are 100 to be mixed with 30 grams of kaolin, add 3.9 grams of sesbania powder, mixing
Uniformly.68.6 grams of phosphate aqueous solutions that phosphoric acid quality percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C6.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (20：80), weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 550 DEG C of temperature.
After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 88%, T60 is 1250 hours.
【Embodiment 8】
Weigh the ZSM-23 that 50 grams of silica alumina ratios are 100 to be mixed with 50 grams of aluminum oxide, add 3.9 grams of sesbania powder, mixing
Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C6.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (60：40), weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 0.5MPa, flow 50ml min-1, 450 DEG C of temperature.
After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 87%, T60 is 1086 hours.
【Embodiment 9】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 100 to be mixed with 35 grams of gama-aluminas, add 2.7 grams of sesbania powder, mix
Close uniform.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C9.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 3- methyl four
Hydrogen furans+water (10：90), weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.Instead
After should terminating, 3- methyltetrahydrofurans conversion ratio is that 94%, T60 is 1050 hours.
【Embodiment 10】
Weigh the Y molecular sieve that 35 grams of silica alumina ratios are 6 to be mixed with 35 grams of gama-aluminas, add sodium carboxymethylcellulose
2.7 grams, it is well mixed.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.
Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C10.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (50：50), weight space velocity 1.8 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 420 DEG C of temperature.
After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 92%, T60 is 1182 hours.
【Embodiment 11】
Weigh the Y molecular sieve that 60 grams of silica alumina ratios are 8 to be mixed with 40 grams of gama-aluminas, add 3.9 grams of sesbania powder, mix
Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C11.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 3- methyl
Tetrahydrofuran+water (50：50), weight space velocity 2.2 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 480 DEG C of temperature.
After reaction terminates, 3- methyltetrahydrofurans conversion ratio is that 90%, T60 is 1182 hours.
【Embodiment 12】
Weigh the Y molecular sieve that 70 grams of silica alumina ratios are 8 to be mixed with 30 grams of boehmites, add 3.9 grams of sesbania powder, mix
Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C12.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- bis-
Methyltetrahydrofuran+water (50：50), weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 3.0MPa, flow 50ml min-1, temperature 400
℃.After reaction terminates, 2,5- dimethyl-tetrahydrofuran conversion ratios are that 91%, T60 is 1283 hours.
【Embodiment 13】
Weigh the Y molecular sieve that 80 grams of silica alumina ratios are 8 to be mixed with 20 grams of boehmites, add 3.9 grams of sesbania powder, mix
Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C13.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- bis-
Methyltetrahydrofuran+water (50：50), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature 350
℃.After reaction terminates, 2,5- dimethyl-tetrahydrofuran conversion ratios are that 88%, T60 is 1084 hours.
【Embodiment 14】
Weigh the Beta molecular sieves that 50 grams of silica alumina ratios are 30 to be mixed with 50 grams of boehmites, add sesbania powder 3.9
Gram, it is well mixed.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.
Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C15.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,4- bis-
Methyltetrahydrofuran+water (50：50), weight space velocity 10.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature
400℃.After reaction terminates, 2,4- dimethyl-tetrahydrofuran conversion ratios are that 95%, T60 is 990 hours.
【Embodiment 15】
Weigh the Beta molecular sieves that 60 grams of silica alumina ratios are 50 to be mixed with 40 grams of boehmites, add sesbania powder 3.9
Gram, it is well mixed.68.6 grams of acetic acid aqueous solutions that quality of acetic acid percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.
Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C15.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,3- bis-
Methyltetrahydrofuran+water (80：20), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature 600
℃.After reaction terminates, 2,3- dimethyl-tetrahydrofuran conversion ratios are that 97%, T60 is 1092 hours.
【Embodiment 16】
Weigh the Beta molecular sieves that 70 grams of silica alumina ratios are 100 to be mixed with 30 grams of boehmites, add sesbania powder 3.9
Gram, it is well mixed.68.6 grams of acetic acid aqueous solutions that quality of acetic acid percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.
Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C16.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,3- bis-
Methyltetrahydrofuran+water (80：20), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature 450
℃.After reaction terminates, 2,3- dimethyl-tetrahydrofuran conversion ratios are that 98%, T60 is 991 hours.
【Embodiment 17】
Weigh the MCM-41 that 50 grams of silica alumina ratios are 20 to be mixed with 50 grams of boehmites, add 3.9 grams of sesbania powder, mix
Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C17.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,3- bis-
Methyltetrahydrofuran+water (0.1：99.9), weight space velocity 0.8 hour-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature
320℃.After reaction terminates, 2,3- dimethyl-tetrahydrofuran conversion ratios are that 85%, T60 is 982 hours.
【Embodiment 18】
Weigh the MCM-22 that 50 grams of silica alumina ratios are 50 to be mixed with 50 grams of boehmites, add 3.9 grams of sesbania powder, mix
Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged
Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C18.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Tetrahydrofuran+water (80：20), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.
After reaction terminates, 2- methyltetrahydrofurans conversion ratio is that 91%, T60 is 1088 hours.
Table 1
Claims (18)
1. a kind of method of aromatisation production aromatic hydrocarbon, including in the presence of water, raw material is with catalyst in aromatization condition
Lower contact and the step of manufacture aromatic hydrocarbon；Wherein, the raw material has structure formula (I)：
In formula (I), R1And R2The C for hydrogen, optionally substituted1-20Straight or branched alkyl, the C optionally substituted2-20Straight or branched alkene
Base, the C optionally substituted2-20Straight or branched alkynyl, the C optionally substituted3-20Cycloalkyl or the C optionally substituted6-20Aryl.
2. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that in formula (I), R1And R2For hydrogen, appoint
Choose the C in generation2-10Straight or branched alkyl, the C optionally substituted2-10Straight or branched alkenyl.
3. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that the dosage of the water is：The matter of water
Amount fraction accounts for the 0.01~99.99% of the gross mass of water and the raw material with structure formula (I).
4. the method for aromatisation production aromatic hydrocarbon according to claim 3, it is characterised in that the dosage of the water is：The matter of water
Amount fraction accounts for the 1~90% of the gross mass of water and the raw material with structure formula (I).
5. the method for aromatisation production aromatic hydrocarbon according to claim 4, it is characterised in that the dosage of the water is：The matter of water
Amount fraction accounts for the 10~60% of the gross mass of water and the raw material with structure formula (I).
6. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that the catalyst is molecular sieve, institute
Molecular sieve is stated in ZSM types molecular sieve, Y type molecular sieve, Beta types molecular sieve, L-type molecular sieve or MCM type molecular sieves at least
It is a kind of.
7. the method for aromatisation production aromatic hydrocarbon according to claim 6, it is characterised in that the molecular sieve is molecule screen banks
Compound, in terms of parts by weight, it includes following component：
A) 20~80 parts of the molecular sieve；
B) 20~80 parts of binding agent.
8. the method that aromatic hydrocarbon is produced according to the aromatisation of claim 6 or 7, it is characterised in that the molecular sieve is selected from ZSM-
5th, at least one of ZSM-11, ZSM-23, ZSM-38, Y, Beta, MCM-22 or MCM-41 molecular sieve.
9. according to claim 8 aromatisation production aromatic hydrocarbon method, it is characterised in that the molecular sieve be selected from ZSM-5,
Y, at least one of Beta or MCM-41 molecular sieves.
10. the method for aromatisation production aromatic hydrocarbon according to claim 6, it is characterised in that the silicon of the ZSM types molecular sieve
Al mole ratio SiO2/Al2O3=10~500；The silica alumina ratio SiO of Y type molecular sieve2/Al2O3=2~70；Beta type molecular sieves
Silica alumina ratio SiO2/Al2O3=10~150；The silica alumina ratio SiO of MCM type molecular sieves2/Al2O3=20~250；L-type
The silica alumina ratio SiO of molecular sieve2/Al2O3=5~100.
11. the method for aromatisation production aromatic hydrocarbon according to claim 10, it is characterised in that the sial of ZSM type molecular sieves rubs
You compare SiO2/Al2O3=15~100；The silica alumina ratio SiO of Y type molecular sieve2/Al2O3=3~50；The silicon of Beta type molecular sieves
Al mole ratio SiO2/Al2O3=15~65；The silica alumina ratio SiO of MCM type molecular sieves2/Al2O3=40~150；L-type molecular sieve
Silica alumina ratio SiO2/Al2O3=6~35.
12. the method for aromatisation production aromatic hydrocarbon according to claim 6, it is characterised in that it is molten that the binding agent is selected from silicon
At least one of glue, boehmite, aluminum oxide, kaolin, montmorillonite or bentonite.
13. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that the aromatization condition bag
Include：300~800 DEG C, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure of reaction temperature, raw material weight air speed 0.3~10 hour-1。
14. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that the raw material biomass derived
Material.
15. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that the raw material is derived from xylose
At least one of alcohol, glucose, cellobiose, cellulose, hemicellulose and lignin；Or derived from paper mill sludge, useless
At least one of paper, bagasse, glucose, timber, corncob, corn stalk and rice straw.
16. the method for aromatisation production aromatic hydrocarbon according to claim 1, it is characterised in that methods described also includes making biology
Material carries out catalyzed conversion, the step of obtaining the raw material.
17. a kind of manufacture method of paraxylene, comprises the following steps：
The step of aromatic hydrocarbon being manufactured according to the method described in claim any one of 1-16；With
The step of paraxylene being isolated from the aromatic hydrocarbon.
18. a kind of manufacture method of terephthalic acid (TPA), comprises the following steps：
The step of manufacturing paraxylene in accordance with the method for claim 17；With
The step of paraxylene is converted into terephthalic acid (TPA).
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| US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
| US5981819A (en) * | 1996-11-26 | 1999-11-09 | Metallgesellschaft Aktiengesellschaft | Process of generating C3 - and C4 -olefins from a feed mixture containing C4 to C7 olefins |
| CN103664482A (en) * | 2013-12-03 | 2014-03-26 | 浙江大学 | Reaction technology for converting oxygen-containing compound into aromatic hydrocarbons by using moving bed process |
| CN105498828A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparation of light aromatic hydrocarbon by furan compound aromatization |
| CN105498827A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for efficient preparation of biomass based aromatic hydrocarbon |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
| US5981819A (en) * | 1996-11-26 | 1999-11-09 | Metallgesellschaft Aktiengesellschaft | Process of generating C3 - and C4 -olefins from a feed mixture containing C4 to C7 olefins |
| CN103664482A (en) * | 2013-12-03 | 2014-03-26 | 浙江大学 | Reaction technology for converting oxygen-containing compound into aromatic hydrocarbons by using moving bed process |
| CN105498828A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparation of light aromatic hydrocarbon by furan compound aromatization |
| CN105498827A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for efficient preparation of biomass based aromatic hydrocarbon |
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