CN107721790A - The manufacture method of aromatic hydrocarbon - Google Patents

The manufacture method of aromatic hydrocarbon Download PDF

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Publication number
CN107721790A
CN107721790A CN201610651748.7A CN201610651748A CN107721790A CN 107721790 A CN107721790 A CN 107721790A CN 201610651748 A CN201610651748 A CN 201610651748A CN 107721790 A CN107721790 A CN 107721790A
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aromatic hydrocarbon
manufacture method
straight
optionally substituted
molecular sieve
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CN107721790B (en
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孔德金
宋奇
郑均林
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of manufacture method of aromatic hydrocarbon, it is included in alcohol compound R3In the presence of OH, the step of raw material manufactures aromatic hydrocarbon with catalyst being contacted under the conditions of aromatization；Wherein, the raw material has structure formula (I)：In formula (I), R1Selected from the C optionally substituted1‑20Straight or branched alkylidene, the C optionally substituted2‑20Straight or branched alkenylene, the C optionally substituted2‑20Straight or branched alkynylene, the C optionally substituted3‑20Cycloalkylidene and the C optionally substituted6‑20Arlydene；R2The C selected from hydrogen, optionally substituted1‑20Straight or branched alkyl and carboxyl；R3For the C optionally substituted1‑20Straight or branched alkyl, the C optionally substituted2‑20Straight or branched alkenyl, the C optionally substituted3‑20Straight or branched cycloalkyl.

Description

The manufacture method of aromatic hydrocarbon
Technical field
The present invention relates to a kind of manufacture method method of aromatic hydrocarbon, particularly a kind of method of manufacture BTX aromatic hydrocarbon.The present invention The method that paraxylene and terephthalic acid (TPA) are manufactured further to the manufacture method based on the aromatic hydrocarbon.
Background technology
Aromatic hydrocarbon product is widely used in the numerous areas such as polyester, chemical fibre, rubber, medicine and fine chemistry industry, domestic consumption Measure considerable, there is material impact to the national economic development, while be the important basic organic chemical industry raw material of social development.Benzene, first Benzene, dimethylbenzene are widely used three kinds of aromatic hydrocarbons bulk chemicals in aromatic hydrocarbons, are referred to as lightweight aromatic hydrocarbon or BTX aromatic hydrocarbon.Benzene It is a kind of basic petrochemical material of multipurpose, its derivative numerous product, including ethyl benzene/styrene, cumene/phenol can be produced Etc..Paraxylene passes through terephthalic acid (TPA) (PTA) or diethyl terephthalate mainly for the manufacture of terephthalic acid (TPA) (DMT) intermediate, for producing poly- cruel fiber such as polyethylene terephthalate (PET), resin and film.At present both at home and abroad The production of aromatic hydrocarbons depends on non-renewable fossil resource, such as by a catalyst by oil by hydrogenation, reform, The technical process such as aromatic hydrocarbons conversion and separation obtains.But because fossil resource reserves finite sum is non-renewable so that with oil More see for the main cost for refining raw material production aromatic hydrocarbons surging.In addition, the utilization of continually developing of fossil resource produces a large amount of greenhouses Gas discharges, and caused a series of environmental problems is on the rise.Therefore, develop (outstanding from renewable resource route production aromatic hydrocarbons It is BTX aromatic hydrocarbon) technology it is significant.
As renewable resource, using biological material as raw material come manufacture aromatic hydrocarbon be current technology study hotspot it One.Prior art is present the report that conversion of biomass material is aromatic hydrocarbon, also discloses that and a variety of uses flat for this purpose Platform compound (such as referring to Katherine Bourzac, From biomass to chemicals in one step, MIT Technology Review,2010-03-29；CN104230615A；US20090227823 and US20110257416A1).
Biomass lactone compound typical case such as valerolactone, can be obtained by cellulose after hydrolyzing deoxidation.Gamma-valerolactone One of biomass platform chemicals have been listed in, gasoline, additive and other chemicals can be converted into by the means of catalysis. For example use H under the noble metal catalyst effect of acid carrier load2Reduction, can obtain valeric acid.Valeric acid by cerium oxide and Decarboxylation coupling reaction can occur for the mixture through catalytic of zirconium oxide, generate butyl ketone, then can obtain gasoline by hydrogenating reduction Component.Use Pd/NbO2Catalyst, at 325 DEG C, 3.5MPa is hydrogenated with to the 50% gamma-valerolactone aqueous solution, and the yield of valeric acid is 92% (J.C.Serrano-Ruiz, D.Wang, J.A.Dumesic, Catalytic upgrading of levulinic acid to 5-nonanone,Green Chemistry 2010,12,574-577.)。
Present inventor is that platform chemicals aromatisation prepares BTX aromatic hydrocarbons patent applied fors (CN with regard to lactone compound 201510345799.2).But found in follow-up R＆D process, C4 alkene in conversion process be present in lactone compound Hydrocarbon intermediate, easily forms polyolefin and carbon distribution, and coking is on catalyst, causing catalyst inactivation and service life short；Meanwhile Because aromatized catalyst inactivates, its aromatizing capacity also drastically declines, and causes the decline of arenes selectivity in final product.For The aromatizing capacity of catalyst is maintained, catalyst needs frequent regeneration.
The content of the invention
The technical problems to be solved by the invention are that alkene thing is unavoidably produced in lactone compound aromatization process Kind, so as to generate carbon distribution, a kind of the problem of causing catalyst inactivation, there is provided manufacture method of new aromatic hydrocarbon.This method can Carbon distribution is effectively removed, recovers the aromatization activity of catalyst, so as to extend the service life of catalyst.
In order to solve the above technical problems, the technical scheme that the present invention takes is as follows：A kind of manufacture method of aromatic hydrocarbon, including In alcohol compound R3In the presence of OH, the step of raw material manufactures aromatic hydrocarbon with catalyst being contacted under the conditions of aromatization； Wherein, the raw material has structure formula (I)：
In formula (I), R1Selected from the C optionally substituted1-20Straight or branched alkylidene, the C optionally substituted2-20Straight or branched Alkenylene, the C optionally substituted2-20Straight or branched alkynylene, the C optionally substituted3-20Cycloalkylidene and the C optionally substituted6-20It is sub- Aryl；R2The C selected from hydrogen, optionally substituted1-20Straight or branched alkyl and carboxyl；
R3For the C optionally substituted1-20Straight or branched alkyl, the C optionally substituted2-20Straight or branched alkenyl, optionally substitution C3-20Straight or branched cycloalkyl.
In above-mentioned technical proposal, in the formula (I), the R1Selected from the C optionally substituted2-10Straight or branched alkylidene The C optionally substituted2-10Straight or branched alkenylene, preferably C2-5Straight or branched alkylidene, further preferred 1,2- Asias second Base.
In above-mentioned technical proposal, in the formula (I), the R2The C selected from hydrogen and optionally substituted1-10Straight or branched alkane Base, it is preferably selected from hydrogen and C1-4Straight or branched alkyl.
In above-mentioned technical proposal, as the compound with lactone groups, gamma-valerolactone can be especially enumerated.
In above-mentioned technical proposal, R3The C preferably optionally substituted1-10Straight or branched alkyl, the C optionally substituted2-10Straight chain Or branched-chain alkenyl, the C that optionally substitutes3-10Straight or branched cycloalkyl.Preferably methanol, ethanol, normal propyl alcohol, isopropanol, butanol, At least one of isobutanol, amylalcohol, hexanol or cyclohexanol.
In above-mentioned technical proposal, the dosage of the alcohol compound is：The mass fraction of alcohol compound accounts for alcohols chemical combination Thing and with structure formula (I) raw material gross mass 0.01~99.99%, preferably 1~90%, more preferably 10~ 60%.
In above-mentioned technical proposal, the catalyst is molecular sieve, and the molecular sieve is selected from ZSM types molecular sieve, Y type molecules At least one of sieve, Beta types molecular sieve, L-type molecular sieve or MCM type molecular sieves.
In above-mentioned technical proposal, the molecular sieve is preferably combination of molecular sieve, and in terms of parts by weight, it is included with the following group Part：
A) 20~80 parts of the molecular sieve；
B) 20~80 parts of binding agent.
In above-mentioned technical proposal, the molecular sieve is selected from ZSM-5, ZSM-11, ZSM-23, ZSM-38, Y, Beta, MCM-22 Or at least one of MCM-41 molecular sieves；Preferably at least one of ZSM-5, Y, Beta or MCM-41 molecular sieve.
In above-mentioned technical proposal, the silica alumina ratio SiO of the ZSM types molecular sieve2/Al2O3=10~500；Preferably SiO2/Al2O3=15~100.
In above-mentioned technical proposal, the silica alumina ratio SiO of Y type molecular sieve2/Al2O3=2~70；Preferably SiO2/Al2O3 =3~50.
In above-mentioned technical proposal, the silica alumina ratio SiO of Beta type molecular sieves2/Al2O3=10~150；Preferably SiO2/ Al2O3=15~65.
In above-mentioned technical proposal, the silica alumina ratio SiO of MCM type molecular sieves2/Al2O3=20~250；Preferably SiO2/ Al2O3=40~150.
In above-mentioned technical proposal, the silica alumina ratio SiO of L-type molecular sieve2/Al2O3=5~100, preferably SiO2/Al2O3 =6~35.
In above-mentioned technical proposal, the binding agent be selected from Ludox, boehmite, aluminum oxide, kaolin, montmorillonite or At least one of bentonite.
In above-mentioned technical proposal, the aromatization condition includes：300~800 DEG C of reaction temperature, preferably 300~650 ℃；Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, preferably 0.5~4MPa；Raw material weight air speed 0.3~10 hour-1；It is preferred that 0.5~ 5 hours-1。
In above-mentioned technical proposal, the raw material biomass derived material.As the biological material, for example can lift Go out this area conventionally used for aromatic hydrocarbon manufacture purposes those, specifically can such as enumerate xylitol, glucose, cellobiose, Cellulose, hemicellulose and lignin etc..These biological materials can be used alone, can also combination of two or more make With.
In above-mentioned technical proposal, as the biological material, paper mill sludge, waste paper, sweet specifically can also be such as enumerated Bagasse, glucose, timber, corncob, corn stalk and rice straw etc..These biological materials can be used alone, can also Combination of two or more uses.Here, by weight percentage, content of cellulose is usually 30- in the biological material 99%, hemicellulose level is usually 0-50%, and content of lignin is usually 0 or 1-40%.
In above-mentioned technical proposal, in addition to biological material is set to carry out catalyzed conversion, the step of obtaining the raw material.
Combination of molecular sieve described in the inventive method can be directly using commercially available prod or according to known in the art Method manufactured.Specifically, the manufacture method as the combination of molecular sieve, for example following methods can be enumerated： By molecular sieve, binding agent and the extrusion aid used as needed, expanding agent and water kneading resulting mixture, extruded moulding, Ran Hou 100~200 DEG C of dryings 1~24 hour, are calcined 1~10 hour at 400~700 DEG C.As the extrusion aid, such as can be with Enumerate those commonly used in the art such as sesbania powder, polyethylene glycol or sodium carboxymethylcellulose；And the expanding agent is used as, than As can enumerate citric acid, oxalic acid or ethylenediamine tetra-acetic acid etc. it is commonly used in the art.In general, extrusion aid and expansion The addition total amount of hole agent is no more than the 10wt% of the gross weight of the mixture.As needed, acid can also be added during shaping.Make For the acid, for example inorganic acid, acetic acid or its aqueous solution etc., the particularly aqueous solution of nitric acid, sulfuric acid or phosphoric acid can be enumerated.One As for, the addition of the sour aqueous solution accounts for 50~90wt% of the gross weight of the mixture.
According to an embodiment of the invention, to there are lactone groups using the biological material as described in raw material derivative The method of compound there is no particular limitation, those conventionally known in the art can be used.For example, the derivative side Method can such as include making the biological material carry out catalyzed conversion (for example hydrolyzing deoxidation), directly have lactone described in manufacture The step of compound (particularly gamma-valerolactone) of group (for example may refer to Direct conversion of cellulose to levulinic acid and gamma-valerolactone using solid acid Catalysts, Catal.Sci.Technol., 2013,3,927-931；Production of levulinic acid and gamma-valerolactone(GVL)from cellulose using GVL as a solvent in biphasic Systems, Energy Environ.Sci., 2012,5,8199-8203).
Contact procedure described in the inventive method can be carried out in one or more reactors.As the reactor, For example hearth reactor can be enumerated, particularly fixed bed reactors, fluidized-bed reactor, fluidized bed reactor or its combination. Now, the mode of operation of the reactor both can be the mode of interval or continuous mode, not limit particularly It is fixed.
Manufacture method according to foregoing aromatic hydrocarbon produces aromatic hydrocarbon as product.In general, in the aromatic hydrocarbon In product, by weight percentage, the content of BTX aromatic hydrocarbon accounts for more than the 60% of gross weight, especially, benzene content be 5.0~ 10.0%, toluene level is 30.0~40.0%, and xylene content is 28.0~40.0%, and remaining is non-aromatic hydrocarbon and weight fragrance Hydrocarbon.The heavy aromatic hydrocarbon refers to carbon nine and its aromatic hydrocarbon of the above.
After aromatic hydrocarbon is produced as product according to the foregoing aromatization method of the present invention, pass through separation, you can from Paraxylene is isolated in the aromatic product.In consideration of it, the invention further relates to a kind of manufacture method of paraxylene, it includes The step of aromatic hydrocarbon being manufactured according to the aromatization method of the present invention；The step of with paraxylene is isolated from the aromatic hydrocarbon.
It is not special to method that paraxylene is isolated from the aromatic hydrocarbon as an embodiment of the invention Restriction, can directly be applicable those conventionally known in this area.
As an embodiment of the invention, can be manufactured pair using the paraxylene of the foregoing manufacture of the present invention as raw material Phthalic acid.In consideration of it, the invention further relates to a kind of manufacture method of terephthalic acid (TPA), it is included according to foregoing pair of the present invention The step of manufacture method manufacture paraxylene of dimethylbenzene；The step of with paraxylene is converted into terephthalic acid (TPA).
It is not special to method that paraxylene is converted into terephthalic acid (TPA) as an embodiment of the invention Limit, can directly be applicable those conventionally known in this area.
To describe the result of the present invention, in the context of the present specification, using T60 as evaluation index.T60 indexs are Refer to, as reaction is carried out, the selectivity of BTX aromatic hydrocarbons is reduced to for 60% reaction time in end-product.For example, work as T60=10, Illustrate reaction after 10 hours, the selectivity of BTX aromatic hydrocarbons drops to 60% in product；As T60=1000, show to react After 1000 hours, the selectivity of BTX aromatic hydrocarbons drops to 60% in product.Index T60 numerical value is bigger, shows catalyst Anti-carbon performance is better, and usage time is longer.
The inventive method has preferable effect to the service life for extending aromatized catalyst, solves biomass aromatic hydrocarbons During aromatized catalyst easy in inactivation, the problem of needing frequent regeneration.Using the inventive method, existed by introducing alcohol compound The water generated in course of reaction in hydroxyl subtractive process carrys out the carbon distribution in situ for removing and being generated in dereaction, can preferably maintain catalyst Activity, extend its life-span, reach the purpose for reducing its regeneration times, feed stock conversion can reach 99%, the T60 of aromatic hydrocarbons Up to 1301 hours, preferable technique effect is achieved.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Comparative example】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 25 to be mixed with 35 grams of gama-aluminas, add 2.7 grams of sesbania powder, mixing Uniformly.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Obtain catalyst Precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C1.
Catalyst activity evaluation is carried out on a fixed bed, reaction condition：Catalyst quality is 3 grams, and reaction substrate is in third Ester, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.Propiolactone conversion ratio is 93%, T60 are 56 hours.
【Embodiment 1】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 25 to be mixed with 35 grams of gama-aluminas, add 2.7 grams of sesbania powder, mixing Uniformly.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Obtain catalyst Precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C1.
Catalyst activity evaluation is carried out on a fixed bed, reaction condition：Catalyst quality is 3 grams, and reaction substrate is in third Ester+methanol (50/50), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.In third Ester conversion rate is that 93%, T60 is 1201 hours.
【Embodiment 2】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 50 to be mixed with 35 grams of boehmites, add 2.7 grams of sesbania powder, mix Close uniform.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C2.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is butyrolactone + ethanol (50/50), weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Butyrolactone Conversion ratio is that 99%, T60 is 1132 hours.
【Embodiment 3】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 150 to be mixed with 35 grams of boehmites, add 2.7 grams of sesbania powder, mix Close uniform.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C3.
60 grams of corn stalks are weighed, is placed in autoclave pressure and adds 700 grams of water, add the 5mol/L of water quality 7% sulphur Acid solution, it is warming up at 180 DEG C and reacts 45 minutes, cool down afterwards, by the reacting liquid filtering after cooling, obtain filter cake and filtering Liquid, filtered fluid are the hydrolyzate of cellulose, after reaction terminates, use mass spectrum to carry out identifying primary product for acetyl to reaction result Propionic acid, its yield are 18 grams.Obtained levulic acid is in fixed bed in the Cu/SiO of 20% content of metal2On be hydrogenated with To gamma-valerolactone, conversion ratio 99%, product yield 98%.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+ethanol (60/40), weight space velocity 0.4 hour-1, Hydrogen Vapor Pressure 3.0MPa, flow 50ml min-1, 500 DEG C of temperature.γ- Valerolactone conversion ratio is that 97%, T60 is 1307 hours.
【Embodiment 4】
Weigh the ZSM-5 that 80 grams of silica alumina ratios are 500 to be mixed with 20 grams of boehmites, add 3.9 grams of sesbania powder, mix Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C4.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is Gamma-valerolactone+propyl alcohol (80/20), weight space velocity 5.0 hours-1, Hydrogen Vapor Pressure 2.0MPa, flow 30ml min-1, temperature 380 ℃.Gamma-valerolactone conversion ratio is that 88%, T60 is 1156 hours.
【Embodiment 5】
Weigh the ZSM-38 that 80 grams of silica alumina ratios are 150 to be mixed with 20 grams of Ludox, add 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C5.
50 grams of bagasse are weighed, is placed in autoclave pressure and adds 500 grams of water, add the 5mol/L of water quality 5% salt Acid solution, 1 hour of reaction at 180 DEG C is warming up to, cools down afterwards, by the reacting liquid filtering after cooling, obtains filter cake and filtering Liquid, filtered fluid are the hydrolyzate of cellulose, after reaction terminates, use mass spectrum to carry out identifying primary product for acetyl to reaction result Propionic acid, its yield are 16 grams.Obtained levulic acid is in fixed bed in the Cu/SiO of 20% content of metal2On be hydrogenated with To gamma-valerolactone, conversion ratio 99%, product yield 99%.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+isobutanol (90/10), weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 480 DEG C of temperature. Gamma-valerolactone conversion ratio is that 92%, T60 is 1165 hours.
【Embodiment 6】
Weigh the ZSM-11 that 80 grams of silica alumina ratios are 150 to be mixed with 20 grams of Ludox, add sodium carboxymethylcellulose 3.9 Gram, it is well mixed.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards. Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C6.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+isobutanol (10/90), weight space velocity 1.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 420 DEG C of temperature. Gamma-valerolactone conversion ratio is that 91%, T60 is 1070 hours.
【Embodiment 7】
Weigh the ZSM-11 that 70 grams of silica alumina ratios are 100 to be mixed with 30 grams of kaolin, add 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of phosphate aqueous solutions that phosphoric acid quality percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C6.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+amylalcohol (50/50), weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 550 DEG C of temperature.γ- Valerolactone conversion ratio is that 88%, T60 is 1025 hours.
【Embodiment 8】
Weigh the ZSM-23 that 50 grams of silica alumina ratios are 100 to be mixed with 50 grams of aluminum oxide, add 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C6.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+cyclohexanol (90/10), weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 0.5MPa, flow 50ml min-1, 450 DEG C of temperature. Gamma-valerolactone conversion ratio is that 91%, T60 is 1133 hours.
【Embodiment 9】
Weigh the ZSM-5 that 35 grams of silica alumina ratios are 100 to be mixed with 35 grams of gama-aluminas, add 2.7 grams of sesbania powder, mix Close uniform.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.It is catalyzed Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C9.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, in reaction substrate γ-penta Ester+ethanol (99/1), weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.γ-penta Interior ester conversion rate is that 88%, T60 is 1025 hours.
【Embodiment 10】
Weigh the Y molecular sieve that 35 grams of silica alumina ratios are 6 to be mixed with 35 grams of gama-aluminas, add sodium carboxymethylcellulose 2.7 grams, it is well mixed.48 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards. Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C10.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+cyclohexanol (95/5), weight space velocity 1.8 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 420 DEG C of temperature. Gamma-valerolactone conversion ratio is that 99%, T60 is 1301 hours.
【Embodiment 11】
Weigh the Y molecular sieve that 60 grams of silica alumina ratios are 8 to be mixed with 40 grams of gama-aluminas, add 3.9 grams of sesbania powder, mix Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C11.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is butyrolactone + methanol (98/2), weight space velocity 2.2 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 480 DEG C of temperature.Butyrolactone turns Rate is that 90%, T60 is 1222 hours.
【Embodiment 12】
Weigh the Y molecular sieve that 70 grams of silica alumina ratios are 8 to be mixed with 30 grams of boehmites, add 3.9 grams of sesbania powder, mix Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C12.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+ethanol (97/3), weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 3.0MPa, flow 50ml min-1, 400 DEG C of temperature.γ- Valerolactone conversion ratio is that 93%, T60 is 1127 hours.
【Embodiment 13】
Weigh the Y molecular sieve that 80 grams of silica alumina ratios are 8 to be mixed with 20 grams of boehmites, add 3.9 grams of sesbania powder, mix Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C13.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+isobutanol (90/10), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 350 DEG C of temperature. Gamma-valerolactone conversion ratio is that 98%, T60 is 1217 hours.
【Embodiment 14】
Weigh the beta molecular sieves that 50 grams of silica alumina ratios are 30 to be mixed with 50 grams of boehmites, add sesbania powder 3.9 Gram, it is well mixed.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards. Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C15.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is butyrolactone + methanol (99.9/0.1), weight space velocity 10.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Fourth Interior ester conversion rate is that 98%, T60 is 1058 hours.
【Embodiment 15】
Weigh the beta molecular sieves that 60 grams of silica alumina ratios are 50 to be mixed with 40 grams of boehmites, add sesbania powder 3.9 Gram, it is well mixed.68.6 grams of nitric acid aqueous acids that quality of acetic acid percentage composition is 5.5% are added afterwards, kneading and compacting, are squeezed Bar.Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C15.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is Δ-penta Lactone+ethanol (50/50), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 600 DEG C of temperature.Δ- Valerolactone conversion ratio is that 99%, T60 is 1246 hours.
【Embodiment 16】
Weigh the beta molecular sieves that 70 grams of silica alumina ratios are 100 to be mixed with 30 grams of boehmites, add sesbania powder 3.9 Gram, it is well mixed.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards. Obtain catalyst precarsor to dry 8 hours at 120 DEG C, be calcined 2 hours by 500 DEG C, obtain molecular sieve catalyst C16.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is caprolactone + n-butanol (80/20), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.In oneself Ester conversion rate is that 94%, T60 is 1286 hours.
【Embodiment 17】
Weigh the MCM-41 that 50 grams of silica alumina ratios are 20 to be mixed with 50 grams of boehmites, add 3.9 grams of sesbania powder, mix Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C17.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is decalactone + ethanol (80/20), weight space velocity 0.8 hour-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 320 DEG C of temperature.Decalactone Conversion ratio is that 97%, T60 is 1262 hours.
【Embodiment 18】
Weigh the MCM-22 that 50 grams of silica alumina ratios are 50 to be mixed with 50 grams of boehmites, add 3.9 grams of sesbania powder, mix Close uniform.68.6 grams of aqueous solution of nitric acid that nitric acid weight/mass percentage composition is 5.5%, kneading and compacting, extrusion are added afterwards.Urged Agent precursor is dried 8 hours at 120 DEG C, is calcined 2 hours by 500 DEG C, is obtained molecular sieve catalyst C18.
Catalyst activity evaluation is carried out on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is γ-penta Lactone+methanol (20/80), weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.γ- Valerolactone conversion ratio is that 97%, T60 is 1205 hours.
Table 1

Claims (21)

1. a kind of manufacture method of aromatic hydrocarbon, is included in alcohol compound R3In the presence of OH, raw material is with catalyst in aromatization Under the conditions of the step of contacting and manufacturing aromatic hydrocarbon；Wherein, the raw material has structure formula (I)：
In formula (I), R1Selected from the C optionally substituted1-20Straight or branched alkylidene, the C optionally substituted2-20Straight or branched Asia alkene Base, the C optionally substituted2-20Straight or branched alkynylene, the C optionally substituted3-20Cycloalkylidene and the C optionally substituted6-20Sub- virtue Base；R2The C selected from hydrogen, optionally substituted1-20Straight or branched alkyl and carboxyl；
R3For the C optionally substituted1-20Straight or branched alkyl, the C optionally substituted2-20Straight or branched alkenyl, optionally substitute C3-20Straight or branched cycloalkyl.
2. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that in formula (I), R1Selected from the C optionally substituted2-10 Straight or branched alkylidene and the C optionally substituted2-10Straight or branched alkenylene；R2The C selected from hydrogen and optionally substituted1-10Straight chain Or branched alkyl.
3. the manufacture method of aromatic hydrocarbon according to claim 2, it is characterised in that in formula (I), R1Selected from C2-5Straight or branched Alkylidene；R2Selected from hydrogen and C1-4Straight or branched alkyl.
4. the manufacture method of aromatic hydrocarbon according to claim 2, it is characterised in that in formula (I), R1Selected from 1,2- ethylidene.
5. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that R3For the C optionally substituted1-10Straight or branched Alkyl, the C optionally substituted2-10Straight or branched alkenyl, the C optionally substituted3-10Straight or branched cycloalkyl.
6. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that the dosage of the alcohol compound is：Alcohols The mass fraction of compound accounts for the 0.01~99.99% of the gross mass of alcohol compound and the raw material with structure formula (I).
7. the manufacture method of aromatic hydrocarbon according to claim 6, it is characterised in that the dosage of the alcohol compound is：Alcohols The mass fraction of compound accounts for the 1~90% of the gross mass of alcohol compound and the raw material with structure formula (I).
8. the manufacture method of aromatic hydrocarbon according to claim 7, it is characterised in that the dosage of the alcohol compound is：Alcohols The mass fraction of compound accounts for the 10~60% of the gross mass of alcohol compound and the raw material with structure formula (I).
9. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that the catalyst is molecular sieve, the molecule Screened from least one of ZSM types molecular sieve, Y type molecular sieve, Beta types molecular sieve, L-type molecular sieve or MCM type molecular sieves.
10. the manufacture method of aromatic hydrocarbon according to claim 9, it is characterised in that the molecular sieve is combination of molecular sieve, In terms of parts by weight, it includes following component：
A) 20~80 parts of the molecular sieve；
B) 20~80 parts of binding agent.
11. according to the manufacture method of the aromatic hydrocarbon of claim 9 or 10, it is characterised in that the molecular sieve be selected from ZSM-5, At least one of ZSM-11, ZSM-23, ZSM-38, Y, Beta, MCM-22 or MCM-41 molecular sieve.
12. the manufacture method of aromatic hydrocarbon according to claim 11, it is characterised in that the molecular sieve be selected from ZSM-5, Y, At least one of Beta or MCM-41 molecular sieves.
13. the manufacture method of aromatic hydrocarbon according to claim 9, it is characterised in that the sial mole of the ZSM types molecular sieve Compare SiO2/Al2O3=10~500；The silica alumina ratio SiO of Y type molecular sieve2/Al2O3=2~70；The sial of Beta type molecular sieves Mol ratio SiO2/Al2O3=10~150；The silica alumina ratio SiO of MCM type molecular sieves2/Al2O3=20~250；L-type molecular sieve Silica alumina ratio SiO2/Al2O3=5~100.
14. the manufacture method of aromatic hydrocarbon according to claim 13, it is characterised in that the silica alumina ratio of ZSM type molecular sieves SiO2/Al2O3=15~100；The silica alumina ratio SiO of Y type molecular sieve2/Al2O3=3~50；The sial of Beta type molecular sieves rubs You compare SiO2/Al2O3=15~65；The silica alumina ratio SiO of MCM type molecular sieves2/Al2O3=40~150；The silicon of L-type molecular sieve Al mole ratio SiO2/Al2O3=6~35.
15. the manufacture method of aromatic hydrocarbon according to claim 9, it is characterised in that it is thin that the binding agent is selected from Ludox, plan At least one of diaspore, aluminum oxide, kaolin, montmorillonite or bentonite.
16. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that the aromatization condition includes：Instead Answer 300~800 DEG C, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure of temperature, raw material weight air speed 0.3~10 hour-1。
17. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that the raw material biomass derived material.
18. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that the raw material is derived from xylitol, grape At least one of sugar, cellobiose, cellulose, hemicellulose and lignin；Or derived from paper mill sludge, waste paper, sugarcane At least one of slag, glucose, timber, corncob, corn stalk and rice straw.
19. the manufacture method of aromatic hydrocarbon according to claim 1, it is characterised in that methods described also includes making biological material Carry out catalyzed conversion, the step of obtaining the raw material.
20. a kind of manufacture method of paraxylene, comprises the following steps：
The step of aromatic hydrocarbon being manufactured according to the method described in claim any one of 1-19；With
The step of paraxylene being isolated from the aromatic hydrocarbon.
21. a kind of manufacture method of terephthalic acid (TPA), comprises the following steps：
The step of manufacturing paraxylene in accordance with the method for claim 20；With
The step of paraxylene is converted into terephthalic acid (TPA).
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Citations (2)

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CN104230615A (en) * 2014-08-25 2014-12-24 南京林业大学 Method for preparing aromatic hydrocarbon and cyclopentenone from biomass derivative gamma-valerolactone by catalytic conversion
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CN104230615A (en) * 2014-08-25 2014-12-24 南京林业大学 Method for preparing aromatic hydrocarbon and cyclopentenone from biomass derivative gamma-valerolactone by catalytic conversion
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