CN105498828A - Method for preparation of light aromatic hydrocarbon by furan compound aromatization - Google Patents
Method for preparation of light aromatic hydrocarbon by furan compound aromatization Download PDFInfo
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- CN105498828A CN105498828A CN201410498179.8A CN201410498179A CN105498828A CN 105498828 A CN105498828 A CN 105498828A CN 201410498179 A CN201410498179 A CN 201410498179A CN 105498828 A CN105498828 A CN 105498828A
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Abstract
The invention relates to a method for preparation of light aromatic hydrocarbon by furan compound aromatization, and mainly solves the problem of excessive reliance of previous aromatic hydrocarbon production on fossil resources. According to a technical scheme, a biomass based furan compound is employed for catalytic aromatization to prepare a aromatic hydrocarbon compound, a furan compound is adopted as the substrate, a molecular sieve is taken as the catalyst, the reaction temperature is 300-800DEG C, the hydrogen pressure is 0.1-5MPa, and the weight space velocity is 0.3-10h<-1>. The furan compound is subjected to catalytic aromatization for high selectivity preparation of benzene, toluene, xylene and other aromatic compounds, the raw material conversion rate can reach more than 80%, the selectivity of benzene, toluene, xylene and other target products is greater than 70%. The method avoids the use of fossil resources as raw materials, takes the biomass based furan compound as the raw material to prepare the aromatic hydrocarbon compound, well solves the problem of excessive reliance of aromatic hydrocarbon production on fossil resources, and can be used in the field of preparation of aromatic hydrocarbon from non-fossil resources.
Description
Technical field
The present invention relates to the method for the light aromatic hydrocarbons of a kind of furfuran compound aromatisation system, especially prepare the light aromatics that benzene,toluene,xylene etc. is important.
Background technology
BTX is the abbreviation of this three classes aromatic hydrocarbon substance of benzene, toluene and dimethylbenzene.BTX is the important basic organic chemical industry raw material of social development, himself or multiple product chain can be derived through regenerative ratio, product is widely used in the numerous areas such as polyester, chemical fibre, rubber, medicine and fine chemistry industry, domestic consumption amount reaches up to ten million ton, has material impact to the national economic development.Benzene is the basic petrochemical material of a kind of multipurpose, can produce numerous products that it is derivative, comprise ethyl benzene/styrene, cumene/phenol etc.Paraxylene is mainly for the manufacture of terephthalic acid (TPA), by terephthalic acid (TPA) (PTA) or diethyl terephthalate (DMT) intermediate, for the production of poly-cruel fiber as PETG (PET), resin and film.The at present both at home and abroad production of aromatic hydrocarbons depends on non-renewable fossil resource, as by a catalyst by oil through hydrogenation, reformation, aromatic conversion with the technical process such as to be separated and to obtain.But fossil resource reserves finite sum is non-renewable, making with oil is that the cost mainly refining raw material production aromatic hydrocarbons is more shown in surging.In addition, continually developing of fossil resource utilizes a large amount of greenhouse gas emission of generation, and caused series of environmental problems is on the rise, and therefore develops and using value significant from renewable resource route production aromatic hydrocarbons.
Living beings are natural a kind of renewable resources, mainly refer to the various organisms utilizing air, water, soil etc. to be produced by photosynthesis, broadly comprise plant, animal and microorganism, mainly refer to plant in the narrow sense.Living beings annual output in the whole world is about 2,000 hundred million tons, rich reserves, wide material sources, cheap and easy to get.The extensive concern that the aromatic hydrocarbon product be widely used causes scientific circles and industrial quarters is prepared from reproducible biomass resource.
Currently reported is aromatic hydrocarbons by biomass conversion, and class methods are for turn to synthesis gas (CO+H by complete for living beings thermal cracking gas
2), then prepare aromatic hydrocarbons through F-T synthesis technology, as Fischer-Tropsch high temperature (350 DEG C) synthesis technique of Sasol company exploitation, in product, alkene and Determination of Alkane Content are more than 80%, arene content about 6% (Zhou Congwen etc., Shenhua science and technology, 2010,8 (4): 93-96).From this 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, and aromatic hydrocarbons only accounts for a very little part.Equations of The Second Kind is that Biomass Syngas is converted into methyl alcohol, continues aromatization process afterwards thus obtains aromatic hydrocarbons.As US, P4686312 reports and methyl alcohol and dimethyl ether is converted into the process of aromatic hydrocarbons by multiple reactor, first after methanol conversion being aliphatic hydrocarbon, aromatization turns to aromatic hydrocarbons again, it is long that this process also exists process, the problem that aromatics yield is not high, about have the carbon of 50% to be converted to carbon dioxide but not carbon monoxide in addition in biomass gasification process in biomass material, gasification efficiency is relatively low.Therefore be synthesis gas by biomass conversion, longer through the route steps of F-T synthesis or aromatization of methanol, the not high deficiency of productive rate of aromatic hydrocarbons.
Summary of the invention
One of technical problem to be solved by this invention, the catalyst of the light aromatic hydrocarbons of a kind of furfuran compound aromatisation system is proposed, this catalyst has the feature of micropore and mesopore simultaneously, and this feature shortens the diffusion path of reactant or product, makes reaction while carrying out smoothly, what be beneficial to BTX diffuses out catalyst, molecular sieve pore passage is not easily blocked, reaches suppression coking, the extending catalyst life-span, improve the object of the productive rate of BTX, have the advantages that cost low aromatisation efficiency is high;
Technical problem two to be solved by this invention, the method for the extensive preparation of the catalyst of one of technical problem providing solution, this preparation method has the Acidity remaining molecular sieve, can maintain the activity of catalyst well;
Technical problem three to be solved by this invention, provide a kind of method that catalyst corresponding with solve technical problem two with one of technical solution problem carries out biomass-based compound aromatisation aromatic hydrocarbons, there is energy consumption low, Atom economy is high, wide adaptability, solve the problem that in biomass-making aromatic hydrocarbons process in the past, aromatics yield is low and reactions steps is long, a kind of new method of biomass-making aromatic hydrocarbons is provided.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the catalyst of the light aromatic hydrocarbons of a kind of furfuran compound aromatisation system, it is characterized in that: this catalyst composition comprises molecular sieve and auxiliary agent, molecular sieve accounts for the mass percent of molecular sieve and auxiliary agent gross mass for being more than or equal to 20% and being less than 80%, and auxiliary agent accounts for the mass percent of molecular sieve and auxiliary agent gross mass for being more than or equal to 20% and being less than 80%.
In technique scheme, the selection of catalyst activity component molecular sieve is most important to reaction, one or more in ZSM-5, ZSM-11, ZSM-23, ZSM-38, MCM-22 and MCM-41 molecular sieve of molecular screening.Wherein preferred scheme is ZSM-5 catalyst, and preferred scheme is that molecular sieve catalyst has the micropore of 0.1 ~ 2 nanometer and the mesoporous of 2 ~ 40 nanometers simultaneously further.
In molecular sieve, the intensity of acidic site and quantity have key effect to the productive rate that furfuran compound prepares BTX.Suitable acid strength and acid amount are to being realized by the silica alumina ratio in modulation molecular sieve catalyst.In technique scheme, the silica alumina ratio of described molecular sieve catalyst is in following scope, and ZSM molecular sieve silica alumina ratio is 10 ~ 500, and preferred technical scheme silica alumina ratio is 15 ~ 100; MCM-22 and MCM-41 silica alumina ratio is 20 ~ 250, and preferred technical scheme silica alumina ratio is 40 ~ 150.
In technique scheme, the auxiliary agent in catalyst is selected from Ludox, boehmite, aluminium oxide, titanium colloidal sol or at least one of clay after acid treatment.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of catalyst of above-mentioned technical solution problem one, molecular sieve obtains with mesoporous and molecular sieve that is micropore through alkali treatment, alkali is one or more in inorganic base and organic base, inorganic base comprises NaOH, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, one or more in barium hydroxide, organic base comprises TMAH, tetraethyl ammonium hydroxide, TPAOH, one or more in TBAH or hydroxide guanidine.In the aqueous solution, paper mill wastewater is 0.1 ~ 4mol/L.The preparation of catalyst comprises following steps, and by molecular sieve, auxiliary agent, peptizing agent, pore creating material kneading, extruded moulding, 100 ~ 200 DEG C of dryings 1 ~ 24 hour after shaping, then roasting 1 ~ 10 hour at 400 ~ 700 DEG C, obtain catalyst.
In technique scheme, the peptizing agent in catalyst is at least one in nitric acid, phosphoric acid and acetic acid.
In technique scheme, the pore creating material in catalyst be selected from methylcellulose, sesbania powder and polyethylene glycol one or more, preferred technical scheme is sesbania powder.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the method for the light aromatic hydrocarbons of a kind of furfuran compound aromatisation system, adopt one of technical solution problem and two catalyst, it is characterized in that in reaction system, with biomass-based furfuran compound for substrate, molecular sieve is as catalyst, reaction temperature is 300 ~ 800 DEG C, Hydrogen Vapor Pressure is 0.1 ~ 5MPa, and hydrogen flowing quantity is 3 ~ 500mL/min, and weight space velocity is 0.3 ~ 10 hour
-1, furfuran compound catalytic aromatization highly selective prepares the aromatics such as benzene, toluene and dimethylbenzene, and feed stock conversion reaches more than 70%; The selective of target product such as benzene toluene dimethylbenzene are greater than more than 80%.
In technique scheme, described biomass-based furfuran compound, comprises furans, hydroxymethylfurfural, furfural, 2-methylfuran, 1,5-dimethyl furan, one or more in Isosorbide-5-Nitrae-dimethyl furan.
In technique scheme, reaction temperature is preferably 350-650 DEG C, and Hydrogen Vapor Pressure is preferably 0.1 ~ 4MPa, and weight space velocity is preferably 0.3-4 hour
-1.
Such furyl compounds by cellulose and the compound such as glucose, fructose Dehydration standby, by contrast containing less oxygen atom and hydroxyl isoreactivity functional group, reactivity is relatively low, the generation of the side reactions such as the carbon distribution that easy reduction produces because there is condensation polycondensation between substrate molecule, thus the yield improving target product BTX.
Adopt the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system of the present invention, its molecular sieve quality accounts for 40% ~ 80% of molecular sieve and auxiliary agent quality, molecular sieve comprises the ZSM-5 molecular sieve of alkali treatment, auxiliary agent is gama-alumina, the mass fraction accounting for molecular sieve and auxiliary agent is 60% ~ 20%, at 350 ~ 500 DEG C, the Hydrogen Vapor Pressure of 0.1 ~ 1MPa, weight space velocity is 0.3 ~ 4 hour
-1technical scheme under, aromatisation dimethyl furan, conversion ratio is the selective of 75%, BTX is 83%.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Take 35 grams of silica alumina ratios be 500 ZSM-5 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, wherein, reaction substrate conversion ratio is the selective of 47%, BTX is 64%.
[embodiment 2]
Take 35 grams of silica alumina ratios be 100 ZSM-5 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C2.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 53%, BTX is 69%.
[embodiment 3]
Take 35 grams of silica alumina ratios be 50 ZSM-5 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C3.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 59%, BTX is 73%.
[embodiment 4]
Take 35 grams of silica alumina ratios be 38 ZSM-5 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C4.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 61%, BTX is 59%.
[embodiment 5]
Take 35 grams of silica alumina ratios be 50 ZSM-5 mix with 35 grams of Ludox auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C5.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 52%, BTX is 46%.
[embodiment 6]
Take 56 grams of silica alumina ratios be 50 ZSM-5 mix with 14 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C6.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is furfural, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 61%, BTX is 81%.
[embodiment 7]
Take 56 grams of silica alumina ratios be 50 ZSM-5 mix with 14 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C7.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2-methylfuran, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 58%, BTX is 76%.
[embodiment 8]
Take 35 grams of silica alumina ratios be 50 ZSM-11 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C8.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 53%, BTX is 76%.
[embodiment 9]
Take 35 grams of silica alumina ratios be 50 ZSM-23 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C9.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 46%, BTX is 68%.
[embodiment 10]
Take 35 grams of silica alumina ratios be 50 ZSM-38 mix with 35 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C10.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 41%, BTX is 56%.
[embodiment 11]
Take 49 grams of silica alumina ratios be 100 MCM-41 mix with 21 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C3.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 48%, BTX is 53%.
[embodiment 12]
Take 49 grams of silica alumina ratios be 100 MCM-22 mix with 21 grams of gama-alumina auxiliary agents, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C3.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, reaction substrate conversion ratio is the selective of 42%, BTX is 56%.
[embodiment 13]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the NaOH solution of 500 milliliters of 0.1mol/L, and 60 DEG C are stirred 4 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C13.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 63%, BTX is 76%.
[embodiment 14]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the NaOH solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C14.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 74%, BTX is 86%.
[embodiment 15]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the NaOH solution of 500 milliliters of 1.0mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C15.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 66%, BTX is 76%.
[embodiment 16]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the NaOH solution of 500 milliliters of 1.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C16.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 45%, BTX is 72%.
[embodiment 17]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the KOH solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C17.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 68%, BTX is 80%.
[embodiment 18]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the LiOH solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C18.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 60%, BTX is 79%.
[embodiment 19]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds the Na of 500 milliliters of 0.5mol/L
2cO
3in solution, 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C19.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 52%, BTX is 75%.
[embodiment 20]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the ammonia spirit of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C20.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 55%, BTX is 72%.
[embodiment 21]
What the ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios added 500 milliliters of 0.5mol/L is in tetramethyl ammonium hydroxide solution, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C21.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 66%, BTX is 79%.
[embodiment 22]
What the ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios added 500 milliliters of 0.5mol/L is in tetraethyl ammonium hydroxide solution, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C22.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 64%, BTX is 78%.
[embodiment 23]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the TPAOH solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C23.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 67%, BTX is 77%.
[embodiment 24]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds in the hydroxide guanidine solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C24.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 75%, BTX is 83%.
[embodiment 25]
The ZSM-5 molecular sieve being 50 by 50 grams of silica alumina ratios adds 500 milliliters of mixed ammonium/alkali solutions, aqueous slkali is the mixed solution of the hydroxide guanidine of the 0.5mol/L of 250 milliliters and the sodium hydrate aqueous solution of 250 milliliters of 0.5mol/L, 80 DEG C are stirred 6 hours, cold water cooling immediately, filter, washing is to neutral rear dry.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 gram molecule sieves and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C25.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 71%, BTX is 84%.
[comparative example 1]
Comparative example 1 is used for illustrating the performance of the synthesis of catalyst of 5A type main active component, the preparation of catalyst and corresponding 2,5-dimethyl furan aromatisation thereof.Concrete reactant ratio and experimental technique as follows:
Take 5A molecular sieve and 35 grams of gama-alumina auxiliary agent mixing that 35 grams of silica alumina ratios are 2, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C5A.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 13%, BTX is 21%.
[comparative example 2]
Comparative example 1 is used for illustrating containing the 5A type molecular sieve of central hole structure to be the performance of the synthesis of the catalyst of main active component, the preparation of catalyst and corresponding 2,5-dimethyl furan aromatisation thereof.Concrete reactant ratio and experimental technique as follows:
The A molecular sieve being 8 by 50 grams of silica alumina ratios adds in the NaOH solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 5A molecular sieve and 35 grams of gama-alumina auxiliary agent mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5% afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst C5A-M.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 11%, BTX is 27%.
[comparative example 3]
Be 35 grams of X molecular sieves and 35 grams of gama-alumina mixing of 8 by silica alumina ratio, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid containing 4.4 grams of red fuming nitric acid (RFNA)s afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst CX.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 16%, BTX is 38%.
[comparative example 4]
The X molecular sieve being 2 by 50 grams of silica alumina ratios adds in the NaOH solution of 500 milliliters of 0.5mol/L, and 80 DEG C are stirred 6 hours, and cold water cooling immediately, filters, dry after washing is extremely neutral.And then after adopting the ammonium nitrate solution of 500 milliliters of 0.5mol/L to exchange three times at 550 DEG C roasting 2h.Take the 35 grams of X molecular sieves and 35 grams of gama-alumina mixing as above prepared, add 2.7 grams, sesbania powder, mix.Add 48 grams of aqueous solution of nitric acid containing 4.4 grams of red fuming nitric acid (RFNA)s afterwards, kneading and compacting, extrusion.Obtain catalyst precarsor at 120 DEG C dry 8 hours, through 500 DEG C of roastings 2 hours, obtain molecular sieve catalyst CX-M.Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is 2,5-dimethyl furan, weight space velocity 1.0 hours
-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin
-1, temperature 400 DEG C.After reaction terminates, calculate reaction result and show that reaction substrate conversion ratio be the selective of 13%, BTX is 42%.
It is the data result of embodiment 1 ~ 25 and comparative example 1 ~ 4 in table 1.
Table 1
Claims (10)
1. the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system, it is characterized in that: this catalyst composition comprises molecular sieve and auxiliary agent, molecular sieve accounts for the mass percent of molecular sieve and auxiliary agent gross mass for being more than or equal to 20% and being less than 80%, and auxiliary agent accounts for the mass percent of molecular sieve and auxiliary agent gross weight for being more than or equal to 20% and being less than 80%;
Wherein one or more in ZSM-5, ZSM-11, ZSM-23, ZSM-38, MCM-22 and MCM-41 molecular sieve of molecular screening.
2. the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 1, is characterized in that: described molecular sieve catalyst has the feature of the micropore of 0.1 ~ 2 nanometer and the meso-hole structure of 2 ~ 40 nanometers simultaneously.
3. the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 1, it is characterized in that: the silica alumina ratio of described molecular sieve catalyst is in following scope: ZSM type molecular sieve silica alumina ratio is the silica alumina ratio of 10 ~ 500, MCM-22 and MCM-41 is 20 ~ 250.
4. the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 3, it is characterized in that the silica alumina ratio of described molecular sieve catalyst is in following scope, ZSM type molecular sieve silica alumina ratio is 15 ~ 100, MCM-22 and MCM-41 silica alumina ratio is 40 ~ 150.
5. the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 1, is characterized in that: the auxiliary agent in catalyst is selected from Ludox, boehmite, aluminium oxide or at least one of clay after acid treatment.
6. the preparation method of the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system described in a Claims 1 to 5, it is characterized in that: first the molecular sieve in catalyst obtains with mesoporous and molecular sieve that is micropore through alkaline solution treatment, alkali in aqueous slkali is one or more in inorganic base and organic base, inorganic base comprises NaOH, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, organic base comprises TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH or hydroxide guanidine, the concentration of aqueous slkali is 0.1 ~ 4mol/L.
7. the preparation method of the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 6, its step comprises: by the molecular sieve after alkali treatment, auxiliary agent, peptizing agent, pore creating material kneading, extruded moulding, 100 ~ 200 DEG C of dryings 1 ~ 24 hour after shaping, then roasting 1 ~ 10 hour at 400 ~ 700 DEG C.
8. the preparation method of the catalyst of the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 6, is characterized in that in the preparation of catalyst, peptizing agent is at least one in nitric acid, phosphoric acid and acetic acid; Pore creating material be selected from methylcellulose, sesbania powder and polyethylene glycol one or more.
9. the method for the light aromatic hydrocarbons of furfuran compound aromatisation system, adopt the catalyst described in claim 1 ~ 8, it is characterized in that, in reaction system, with biomass-based furfuran compound for substrate, reaction temperature is 300 ~ 800 DEG C, and Hydrogen Vapor Pressure is 0.1 ~ 5MPa, hydrogen flowing quantity is 3 ~ 500mL/min, and weight space velocity is 0.3 ~ 10 hour
-1, furfuran compound catalytic aromatization highly selective prepares benzene, toluene and dimethylbenzene aromatic.
10. the method for the light aromatic hydrocarbons of furfuran compound aromatisation system according to claim 9, is characterized in that described biomass-based furfuran compound, comprises furans, 5 hydroxymethyl furfural, furfural, 2-methylfuran, 2,5-dimethyl furan, one or more in Isosorbide-5-Nitrae-dimethyl furan; Described reaction temperature is 350 DEG C ~ 650 DEG C, and Hydrogen Vapor Pressure is 0.1 ~ 4MPa, and weight space velocity is 0.3-4 hour
-1.
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