CN105498825B - Furfuran compound aromatization turns to the method for increasing of aromatic hydrocarbons - Google Patents
Furfuran compound aromatization turns to the method for increasing of aromatic hydrocarbons Download PDFInfo
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- CN105498825B CN105498825B CN201410497689.3A CN201410497689A CN105498825B CN 105498825 B CN105498825 B CN 105498825B CN 201410497689 A CN201410497689 A CN 201410497689A CN 105498825 B CN105498825 B CN 105498825B
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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
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to the method for increasing that a kind of furfuran compound aromatization turns to aromatic hydrocarbons, during solving previous biomass-based production of chemicals aromatic hydrocarbons, the low problem of arenes selectivity.With biomass-based furfuran compound, catalytic aromatization prepares aromatic compound to the present invention with high selectivity, use furfuran compound for substrate, for modified molecular sieve as catalyst, reaction temperature is 300~800 DEG C, Hydrogen Vapor Pressure is 0.1~5MPa, and weight space velocity is 0.3~10 hour‑1Technical solution, furfuran compound catalytic aromatization is prepared into the aromatic compounds such as benzene, toluene and dimethylbenzene with high selectivity, feed stock conversion reaches 65% or more;The selectivity of the target products such as benzene toluene dimethylbenzene is greater than 85% or more.The shape-selective effect that this method is acted synergistically by two-component molecular sieve and further improves catalyst to aromatic hydrocarbons to the silanization treatment of molecular sieve, it preferably solves the problems, such as that arenes selectivity is low in the production of biomass-based aromatic hydrocarbons, can be used for non-fossil sources aromatic hydrocarbons field.
Description
Technical field
The present invention relates to the method for increasing that a kind of furfuran compound aromatization turns to aromatic hydrocarbons, especially raising benzene, toluene, two
The ratio of the important basic organic chemical industry raw material such as toluene in the product.
Background technique
Benzene, toluene and dimethylbenzene are the important basic organic chemical industry raw materials of social development, its own or pass through reproduction
Multiple product chain can be derived, product is widely used in the numerous areas such as polyester, chemical fibre, rubber, medicine and fine chemistry industry, state
Interior consumption figure reaches up to ten million tons, has great influence to the national economic development.Benzene is a kind of basic petrochemical material of multipurpose, can
To produce numerous products, including ethyl benzene/styrene, cumene/phenol etc. derived from it.Paraxylene is mainly for the manufacture of right
Phthalic acid gathers cruel fiber such as producing by terephthalic acid (TPA) (PTA) or diethyl terephthalate (DMT) intermediate
Polyethylene terephthalate (PET), resin and film.These three types of aromatic hydrocarbons are typical light aromatics, are abbreviated as BTX.Mesh
The production of preceding domestic and international BTX depends on non-renewable fossil resource, such as can be by a catalyst by petroleum by adding
The technical process such as hydrogen, reformation, aromatic hydrocarbons conversion and separation obtain.But fossil resource reserves are limited and non-renewable, so that with
Petroleum is that the cost that main refining raw material produces aromatic hydrocarbons is more shown in surging.In addition, continually developing for fossil resource is a large amount of using generating
Greenhouse gas emission, caused a series of environmental problems are on the rise, therefore develop from renewable resource route and produce aromatic hydrocarbons
Significant and application value.
The plant that nature is widely present is a kind of typical renewable resource, belongs to one kind of biomass.Global biology
The annual yield of matter is about 200,000,000,000 tons, and rich reserves are from a wealth of sources, cheap and easy to get.From reproducible biomass resource
It is prepared with the extensive concern that widely applied aromatic hydrocarbon product causes scientific circles and industry.
Currently reported to convert biomass into BTX, a kind of method is that the complete thermal cracking gas of biomass is turned to synthesis
Gas (CO+H2), using F- T synthesis technology prepare BTX, as Sasol company develop Fischer-Tropsch high temperature (350 DEG C) synthesis technology,
Alkene and Determination of Alkane Content are more than 80% in product, arene content about 6% (Zhou Congwen etc., Shenhua science and technology, 2010,8 (4):93-
96).In terms of the process, F- T synthesis can be used as a kind of transform mode of gasification of biomass, but its major product is alkane and alkene
Hydrocarbon, aromatic hydrocarbons only account for small part.Second class is to convert Biomass Syngas to methanol, continues aromatization process later
To obtain aromatic hydrocarbons.Convert methanol and dimethyl ether to by multiple reactors the mistake of aromatic hydrocarbons as US, P 4686312 are reported
Journey, converts methanol into after aliphatic hydrocarbon that aromatization turns to aromatic hydrocarbons again first, and that there is processes is long for the process, and aromatics yield is not high
Problem, in addition the carbon in biomass gasification process in biomass material there are about 50% is converted to carbon dioxide rather than an oxidation
Carbon, gasification efficiency are relatively low.Therefore synthesis gas is converted biomass into, using F- T synthesis or the route of aromatization of methanol
The deficiencies of step is long, and the yield of aromatic hydrocarbons is not high.
Summary of the invention
The first technical problem to be solved by the present invention proposes that a kind of furfuran compound aromatization turns to the catalysis of aromatic hydrocarbons
Agent, the catalyst reduce the surface acidity bit quantity that surface does not have Shape-selective, reduce after silylating reagent is modified
Molecular sieve bore diameter, controls the distribution of aromatic product, improves the selectivity of BTX in product, have aromatisation at low cost high-efficient and
The characteristics of being easy industrialization amplification;
The second technical problem to be solved by the present invention, the catalyst of one of the technical issues of providing solution it is extensive
The method of preparation, the preparation method have does not destroy framework of molecular sieve structure, to product play the role of preferably sieve and it is shape-selective,
It can further improve the selectivity of BTX;
The third technical problem to be solved by the present invention, provides one of one kind and solution technical problem and solution technology is asked
The method that the corresponding catalyst of the two of topic carries out biomass-based compound aromatisation aromatic hydrocarbons, have low energy consumption, atom economy
Property high, wide adaptability, solve the problems, such as that aromatics yield is low and reaction step is long during previous biomass aromatic hydrocarbons, provides one
The new method of kind biomass aromatic hydrocarbons.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows:A kind of furfuran compound aromatization
Turn to the volume increase catalyst of aromatic hydrocarbons, it is characterised in that:The catalyst composition include molecular sieve and auxiliary agent, molecular sieve account for molecular sieve and
The mass percent of auxiliary agent gross mass is more than or equal to 20% and less than 80%, and auxiliary agent accounts for the quality of molecular sieve and auxiliary agent gross mass
Percentage is more than or equal to 20% and less than 80%.
In above-mentioned technical proposal, to reacting most important, molecular sieve is selected from for the selection of catalyst activity component molecular sieve
One of beta, Y, MCM-22, MCM-41 and mordenite molecular sieve or a variety of.Wherein preferred scheme is multiple groups fractionated molecule
Sieve catalyst, molecular sieve are preferably Y molecular sieve and beta molecular sieve.The intensity and quantity of acidic site are to furans in molecular sieve
Closing the yield that object prepares BTX has key effect.Suitable acid strength and acid amount are to can be by modulation molecular sieve catalyst
Silica alumina ratio is realized.In above-mentioned technical proposal, in the following range, beta and mercerising boil the silica alumina ratio of the molecular sieve catalyst
Stone molecular sieve silica alumina ratio is 10~300, and preferred technical solution silica alumina ratio is 10~65;Y molecular sieve, MCM-22 and MCM-41 silicon
Aluminium ratio is 2~250, and preferred technical solution silica alumina ratio is 3~150.When molecular sieve is selected from Y molecular sieve and beta molecular sieve, Y's
Silica alumina ratio is 3~30, and modenite silica alumina ratio is 3~30.
In above-mentioned technical proposal, the auxiliary agent in catalyst is selected from silica solution, boehmite, aluminium oxide or acid treated
At least one of clay.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows:A kind of above-mentioned solution technical problem
The preparation method of one catalyst, comprises the following steps, by molecular sieve, auxiliary agent, peptizing agent, pore creating material kneading, and extruded moulding, at
100~200 DEG C drying 1~24 hour after type, then through roasting 1~10 hour at 400~700 DEG C, obtain catalyst Precursors.
In above-mentioned technical proposal, the peptizing agent in catalyst is at least one of nitric acid, phosphoric acid and acetic acid.
In above-mentioned technical proposal, pore creating material in catalyst in methylcellulose, sesbania powder and polyethylene glycol one
Kind is a variety of, and preferred technical solution is sesbania powder.
In above-mentioned technical proposal, obtained catalyst Precursors are immersed in nonpolar solvent, nonpolar solvent and catalyst
The mass ratio of parent is 1~20, nonpolar solvent be the chain alkane of C5~C10 and one of the cycloalkane of C5~C10 or
It is a variety of, and be added and be selected from one of tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, silicon tetrachloride or a variety of dressing agents
It is reacted, the quality of dressing agent is the 1%~150% of catalyst Precursors quality, it is dry at 80~150 DEG C after processing, and
It is roasted 0.5~8 hour at 300~600 DEG C, obtains catalyst.
To solve above-mentioned technical problem three, the technical solution adopted by the present invention is as follows:A kind of furfuran compound aromatization
The method for increasing for turning to aromatic hydrocarbons, using its two catalyst of one of solution technical problem sum, it is characterised in that in the reaction system,
Using biomass-based furfuran compound as substrate, molecular sieve is 300-800 DEG C as catalyst, reaction temperature, and Hydrogen Vapor Pressure is
0.1~5MPa, hydrogen flowing quantity are 3~500mL/min, and weight space velocity is 0.3~10 hour-1, furfuran compound catalysis aromatization
Change prepares the aromatic compounds such as benzene, toluene and dimethylbenzene with high selectivity, and feed stock conversion reaches 80% or more;Benzene toluene diformazan
The selectivity of the target products such as benzene is greater than 70% or more.
In above-mentioned technical proposal, the biomass-based furfuran compound, including furans, hydroxymethylfurfural, furfural, 2-
Methylfuran, 1,5- dimethyl furan, one of Isosorbide-5-Nitrae-dimethyl furan or a variety of.
In above-mentioned technical proposal, reaction temperature is preferably 300-650 DEG C, and Hydrogen Vapor Pressure is preferably 0.1~4MPa, and weight is empty
Speed preferably 0.3-4 hours-1。
Such furyl compounds is dehydrated by the compounds such as cellulose and glucose, fructose and is prepared, in contrast containing more
Few oxygen atom and hydroxyl isoreactivity functional group, reactivity is relatively low, is easily reduced because being condensed between substrate molecule
Polycondensation and the generation of the side reactions such as carbon distribution for generating, to improve the yield of target product BTX.
The catalyst of aromatic hydrocarbons is turned to using furfuran compound aromatization of the invention, molecular sieve quality accounts for molecular sieve and helps
The 40%~80% of agent quality, molecular sieve include silica alumina ratio 3~20 beta molecule 10~35 of Y molecular sieve and silica alumina ratio
Sieve, auxiliary agent is gama-alumina, and the mass fraction for accounting for molecular sieve and auxiliary agent is 60%~20%, at 350~500 DEG C, 0.1~
The Hydrogen Vapor Pressure of 1MPa, weight space velocity are 0.3~4 hour-1Technical solution under, aromatisation dimethyl furan, conversion ratio is
The selectivity of 68%, BTX are 89%.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
It weighs the Y molecular sieve that 35 grams of silica alumina ratios are 50 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder 2.7 is added
Gram, it is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.?
It is 8 hours dry at 120 DEG C to catalyst precarsor, it is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst.Catalyst activity
Evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- dimethyl furan, weight
Air speed 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, reaction result is shown in Table
1, the selectivity that reaction substrate conversion ratio is 47%, BTX is 64%.
【Embodiment 2】
It weighs the Y molecular sieve that 35 grams of silica alumina ratios are 8 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder 2.7 is added
Gram, it is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.?
It is 8 hours dry at 120 DEG C to catalyst precarsor, it is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst.Catalyst activity
Evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- dimethyl furan, weight
Air speed 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, reaction result is shown in Table
1, the selectivity that reaction substrate conversion ratio is 48%, BTX is 59%.
【Embodiment 3】
It weighs the beta molecular sieve that 35 grams of silica alumina ratios are 20 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder is added
It 2.7 grams, is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.
It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst.Catalyst is living
Property evaluation evaluated on a fixed bed, reaction condition catalyst quality be 3 grams, reaction substrate 2,5- dimethyl furan, weight
Amount air speed 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, reaction result is shown in
Table 1, the selectivity that reaction substrate conversion ratio is 46%, BTX are 56%.
【Embodiment 4】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst.Catalyst activity evaluation is evaluated on a fixed bed, reaction condition
Catalyst quality is 3 grams, reaction substrate 2,5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow
50ml min-1, 400 DEG C of temperature.After reaction, reaction result shows that reaction substrate conversion ratio is that the selectivity of 63%, BTX is
71%.
【Embodiment 5】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 10.5 grams of sial including 24.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst.Catalyst activity evaluation is evaluated on a fixed bed, reaction condition
Catalyst quality is 3 grams, reaction substrate 2,5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow
50ml min-1, 400 DEG C of temperature.After reaction, reaction result shows that reaction substrate conversion ratio is that the selectivity of 67%, BTX is
77%.
【Embodiment 6】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 24.5 grams of sial including 10.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst.Catalyst activity evaluation is evaluated on a fixed bed, reaction condition
Catalyst quality is 3 grams, reaction substrate 2,5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow
50ml min-1, 400 DEG C of temperature.After reaction, reaction result shows that reaction substrate conversion ratio is that the selectivity of 58%, BTX is
76%.
【Embodiment 7】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5-
Dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 66%, BTX is 87%.
【Embodiment 8】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetraethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5-
Dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 64%, BTX is 81%.
【Embodiment 9】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- bis-
Methylfuran, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction,
Reaction result shows that the selectivity that reaction substrate conversion ratio is 68%, BTX is 88%.
【Embodiment 10】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 5- hydroxyl first
Base furfural, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, instead
It answers the result shows that the selectivity that reaction substrate conversion ratio is 66%, BTX is 84%.
【Embodiment 11】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is furfural, weight
Amount air speed 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, reaction result table
The selectivity that bright reaction substrate conversion ratio is 61%, BTX is 82%.
【Embodiment 12】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2- methyl
Furans, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, it reacts
The result shows that the selectivity that reaction substrate conversion ratio is 64%, BTX is 83%.
【Embodiment 13】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is furans, weight
Amount air speed 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, reaction result table
The selectivity that bright reaction substrate conversion ratio is 60%, BTX is 82%.
【Embodiment 14】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is Isosorbide-5-Nitrae-two
Methylfuran, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction,
Reaction result shows that the selectivity that reaction substrate conversion ratio is 68%, BTX is 87%.
【Embodiment 15】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the modenite for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Later plus
Enter 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained to do at 120 DEG C
It dry 8 hours, is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into 5 times of molecular sieve parents
In heptane solvent containing 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and obtain at 550 DEG C at 80 DEG C
Catalyst.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,
5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction knot
Shu Hou, reaction result show that the selectivity that reaction substrate conversion ratio is 62%, BTX is 82%.
【Embodiment 16】
Weighing gross mass is that 35 gram molecules sieve mixture, beta, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 30
It for 20 mercerising, is mixed with 8.75 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5-
Dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 58%, BTX is 78%.
【Embodiment 17】
Weighing gross mass is that 35 gram molecules sieve mixture, beta, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 30
It for 100 MCM-22, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5-
Dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 64%, BTX is 74%.
【Embodiment 18】
Weighing gross mass is that 35 gram molecules sieve mixture, beta, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 30
It for 100 MCM-41, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- bis-
Methylfuran, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction,
Reaction result shows that the selectivity that reaction substrate conversion ratio is 68%, BTX is 77%.
【Embodiment 19】
Weighing gross mass is that 35 gram molecules sieve mixture, mercerising, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 20
It for 50 MCM-41, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- bis-
Methylfuran, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction,
Reaction result shows that the selectivity that reaction substrate conversion ratio is 66%, BTX is 74%.
【Embodiment 20】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 8% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5-
Dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 68%, BTX is 89%.
【Embodiment 21】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 12% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and obtain at 550 DEG C at 80 DEG C
Catalyst.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,
5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 61%, BTX is 82%.
【Embodiment 22】
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 24% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and obtain at 550 DEG C at 80 DEG C
Catalyst.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,
5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that the selectivity that reaction substrate conversion ratio is 67%, BTX is 80%.
【Comparative example 1】
After catalyst in comparative example is by being prepared separately X and 5A molecular sieve, both catalytic mechanicals are mixed to get.
Preparation method is as follows:It weighs the X that 35 grams of silica alumina ratios are 2 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder 2.7 is added
Gram, it is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion are added later.It is urged
Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst X.Weigh 35 grams of sial
It is mixed than the 5A molecular sieve for 8 with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.It is added later
48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion.It is dry at 120 DEG C to obtain catalyst precarsor
It 8 hours, is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst 5A.It is in mass ratio 5 by catalyst X and catalyst 5A:5
It is uniformly mixed, obtains the catalyst of physical mixed.Catalyst activity evaluation is evaluated on a fixed bed, reaction condition catalysis
Agent quality is 3 grams, reaction substrate 2,5- dimethyl furan, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml
min-1, 400 DEG C of temperature.After reaction, reaction result shows that the selectivity that reaction substrate conversion ratio is 19%, BTX is 35%.
【Comparative example 2】
After the mixing of X and 5A molecular sieve will be prepared separately in catalyst in comparative example 2, after being handled using tetramethoxy-silicane
It arrives.Preparation method is as follows:It weighs the X that 35 grams of silica alumina ratios are 2 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder is added
It 2.7 grams, is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion are added later.It obtains
Catalyst precarsor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst X.Weigh 35 grams of silicon
Aluminium is mixed than the 5A molecular sieve for 8 with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, is uniformly mixed.Later plus
Enter 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained to do at 120 DEG C
It dry 8 hours, is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst 5A.It is in mass ratio 5 by catalyst X and catalyst 5A:
5 are uniformly mixed, and obtain the catalyst Precursors of physical mixed.The precursor catalyst 5 times of molecular sieve parents of immersion are contained 4%
In the heptane solvent of tetramethoxy-silicane, 5h is stirred at room temperature.It takes out at 80 DEG C after drying, roasting obtains catalyst at 550 DEG C.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate 2,5- diformazan
Base furans, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, instead
It answers the result shows that the selectivity that reaction substrate conversion ratio is 18%, BTX is 51%.It is Examples 1 to 22 and comparative example in table 1
1,2 data result.
Table 1
Claims (8)
1. the catalyst that a kind of furfuran compound aromatization turns to aromatic hydrocarbons, it is characterised in that:Catalyst composition includes molecular sieve
And auxiliary agent, it is more than or equal to 20% and less than 80% that molecular sieve, which accounts for molecular sieve and the mass percent of auxiliary agent gross mass, and auxiliary agent accounts for
The mass percent of molecular sieve and auxiliary agent total weight is more than or equal to 20% and less than 80%;
Molecular sieve is selected from one of beta, Y, MCM-22, MCM-41 and mordenite molecular sieve or a variety of;
Wherein, the furfuran compound aromatization turns to the preparation method of the catalyst of aromatic hydrocarbons, including:Catalyst preparation step
Including:By molecular sieve, auxiliary agent, peptizing agent, pore creating material kneading, extruded moulding, 100~200 DEG C drying 1~24 hour after molding,
Again through roasting 1~10 hour at 400~700 DEG C, catalyst Precursors are obtained;
Catalyst Precursors are immersed in nonpolar solvent;Wherein, the mass ratio of nonpolar solvent and catalyst Precursors is 1~20,
Nonpolar solvent is C5~C10Chain alkane and C5~C10One of cycloalkane or a variety of, and be added and be selected from tetramethoxy
One of silicon, tetraethoxy-silicane, tetrapropoxy-silicane, silicon tetrachloride or a variety of dressing agents are reacted, and the quality of dressing agent is
The 1%~150% of catalyst Precursors quality, it is dry at 80~150 DEG C after processing, and 0.5~8 is roasted at 300~600 DEG C
Hour, obtain catalyst.
2. the catalyst that furfuran compound aromatization according to claim 1 turns to aromatic hydrocarbons, it is characterised in that:Point
The silica alumina ratio of sub- sieve catalyst is in the following range:Beta and mordenite molecular sieve silica alumina ratio are 10~300, Y molecular sieve,
MCM-22 and MCM-41 molecular sieve silica alumina ratio is 2~250.
3. the catalyst that furfuran compound aromatization according to claim 2 turns to aromatic hydrocarbons, it is characterised in that point
In the following range, beta and mordenite molecular sieve silica alumina ratio are 10~65 to the silica alumina ratio of sub- sieve catalyst, Y molecular sieve,
MCM-22 and MCM-41 silica alumina ratio is 3~150.
4. the catalyst that furfuran compound aromatization according to claim 1 turns to aromatic hydrocarbons, it is characterised in that:In catalyst
Auxiliary agent be selected from silica solution, boehmite, aluminium oxide or acid treated clay at least one.
5. the preparation that furfuran compound aromatization described in a kind of any one of Claims 1 to 4 turns to the catalyst of aromatic hydrocarbons
Method, it is characterised in that:Catalyst preparation step includes:By molecular sieve, auxiliary agent, peptizing agent, pore creating material kneading, extruded moulding,
100~200 DEG C drying 1~24 hour after molding, then through roasting 1~10 hour at 400~700 DEG C, obtain catalyst Precursors;
Wherein, catalyst Precursors are immersed in nonpolar solvent;Wherein, the mass ratio of nonpolar solvent and catalyst Precursors is 1
~20, nonpolar solvent C5~C10Chain alkane and C5~C10One of cycloalkane or a variety of, and be added and be selected from four
One of methoxyl group silicon, tetraethoxy-silicane, tetrapropoxy-silicane, silicon tetrachloride or a variety of dressing agents are reacted, dressing agent
Quality is the 1%~150% of catalyst Precursors quality, dry at 80~150 DEG C after processing, and is roasted at 300~600 DEG C
0.5~8 hour, obtain catalyst.
6. furfuran compound aromatization according to claim 5 turns to the preparation method of the catalyst of aromatic hydrocarbons, feature exists
Peptizing agent is at least one of nitric acid, phosphoric acid and acetic acid in catalyst;Pore creating material is selected from methylcellulose, sesbania powder and gathers
One of ethylene glycol is a variety of.
7. a kind of furfuran compound aromatization turns to the method for increasing of aromatic hydrocarbons, using described in any one of Claims 1 to 4
Furfuran compound aromatization turns to the catalyst of aromatic hydrocarbons, which is characterized in that in the reaction system, with biomass-based furans chemical combination
Object is substrate, and reaction temperature is 300~800 DEG C, and Hydrogen Vapor Pressure is 0.1~5MPa, and hydrogen flowing quantity is 3~500mL/min, weight
Air speed is 0.3~10 hour-1, furfuran compound catalytic aromatization prepares benzene, toluene and dimethylbenzene aromatization with high selectivity
Close object.
8. the method for increasing that furfuran compound aromatization according to claim 7 turns to aromatic hydrocarbons, it is characterised in that described
Biomass-based furfuran compound, including furans, 5 hydroxymethyl furfural, furfural, 2- methylfuran, 2,5- dimethyl furans, 1,
One of 4- dimethyl furan is a variety of.
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US5367099A (en) * | 1993-05-28 | 1994-11-22 | Mobil Oil Corp. | Selective toluene disproportionation process (STDP) with ex situ selectivated zeolite catalyst |
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US5367099A (en) * | 1993-05-28 | 1994-11-22 | Mobil Oil Corp. | Selective toluene disproportionation process (STDP) with ex situ selectivated zeolite catalyst |
CN101811063A (en) * | 2009-02-19 | 2010-08-25 | 中国石油化工股份有限公司 | Catalyst for alkyl transfer and conversion of C9 and C9+ heavy aromatics to light aromatics |
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