CN107586246B - Method for producing aromatic hydrocarbon by aromatization - Google Patents
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- CN107586246B CN107586246B CN201610539618.4A CN201610539618A CN107586246B CN 107586246 B CN107586246 B CN 107586246B CN 201610539618 A CN201610539618 A CN 201610539618A CN 107586246 B CN107586246 B CN 107586246B
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Abstract
The invention relates to a method for producing aromatic hydrocarbon by aromatization, comprising the steps of contacting raw materials with a catalyst under aromatization reaction conditions in the presence of water to produce aromatic hydrocarbon; wherein the starting material has the structural formula (I):
in the formula (I), R1And R2Is hydrogen, optionally substituted C1‑20Straight or branched alkyl, optionally substituted C2‑20Straight or branched alkenyl, optionally substituted C2‑20Straight or branched alkynyl, optionally substituted C3‑20Cycloalkyl or optionally substituted C6‑20And (4) an aryl group.
Description
Technical Field
The invention relates to a method for producing aromatic hydrocarbon by aromatization, in particular to a method for producing BTX aromatic hydrocarbon. The present invention further relates to a process for producing paraxylene and terephthalic acid based on the aromatic hydrocarbon production process.
Background
The aromatic hydrocarbon product is widely applied to the fields of polyester, chemical fiber, rubber, medicine, fine chemical industry and the like, has considerable domestic consumption, has important influence on national economic development, and is an important basic organic chemical raw material for social development. Benzene, toluene and xylene are three bulk chemicals of aromatic hydrocarbons widely used in aromatic hydrocarbons, and are collectively called light aromatic hydrocarbons or BTX aromatic hydrocarbons. Benzene is a versatile basic petrochemical feedstock from which a wide variety of products derived therefrom can be produced, including ethylbenzene/styrene, cumene/phenol, and the like. Para-xylene is used primarily in the manufacture of terephthalic acid, via terephthalic acid (PTA) or diethyl terephthalate (DMT) intermediates, for the production of poly-cool fibers such as polyethylene terephthalate (PET), resins, and films. At present, the production of aromatic hydrocarbon at home and abroad mainly depends on non-renewable fossil resources, and for example, the aromatic hydrocarbon can be obtained by carrying out the processes of hydrogenation, reforming, aromatic hydrocarbon conversion, separation and the like on petroleum on a catalyst. However, the cost of producing aromatics from petroleum as the major refinery feedstock is increasing due to the limited and non-renewable nature of fossil resources. In addition, the continuous development and utilization of fossil resources generate a large amount of greenhouse gas emissions, which causes a series of environmental problems that are becoming serious. Therefore, it is of great interest to develop technologies for the production of aromatics, especially BTX aromatics, from renewable resource routes.
As a renewable resource, the production of aromatic hydrocarbons from biomass materials is one of the hot spots in the current technological research. There are reports of the conversion of biomass materials to aromatics and various platform compounds used for this purpose are also disclosed (see, for example, Katherine Bourzac, From biomass to chemicals in one step, MITTECHNOLOGY Review, 2010-03-29; CN 104230615A; US20090227823 and US20110257416A 1).
Tetrahydrofuran compounds are widely used, typically methyl Tetrahydrofuran (2-MeTHF) and Tetrahydrofuran (THF), a commonly used moderately polar aprotic solvent, its primary use is as precursors for high molecular Polymers, polytetrahydrofuran which polymerizes into chains in a strongly acidic environment, for the manufacture of elastic polyurethane fibers, such as spandex (Polymers, tetrahedron and Oxetane Polymers by Gerfried Pruckmayr, P.Dreyfuss, M.P.Dreyfuss// Kirk-OthEnmer cyclophysis of Chemical technology, John Wiley & Sons, Inc.1996), and also as Industrial solvents in the production of PVC and paints (Herbert M ü, Wilford's environmental Chemistry, Wiley-2002-VCim).
The inventor of the present application has applied for patent (CN201510345862.2) on the aromatization of tetrahydrofuran compounds as a platform compound to prepare BTX aromatic hydrocarbon. However, in the subsequent research and development processes, the tetrahydrofuran compound has a C4 olefin intermediate in the conversion process, which is very easy to form polyolefin and carbon deposition, coke on the catalyst, and cause catalyst deactivation and short service life; meanwhile, because the aromatization catalyst is deactivated, the aromatization capacity of the aromatization catalyst is also sharply reduced, so that the selectivity of aromatic hydrocarbon in a final product is reduced. In order to maintain the aromatization capacity of the catalyst, the catalyst needs to be regenerated frequently.
Disclosure of Invention
The invention aims to solve the technical problem that olefin species are inevitably generated in the aromatization process of tetrahydrofuran compounds, so that carbon deposition is generated to cause the deactivation of a catalyst, and provides a novel method for producing aromatic hydrocarbons by aromatization. The method can effectively remove carbon deposition and recover the aromatization activity of the catalyst, thereby prolonging the service life of the catalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for producing aromatic hydrocarbons by aromatization comprising the step of contacting a feedstock with a catalyst in the presence of water under aromatization reaction conditions to produce aromatic hydrocarbons; wherein the starting material has the structural formula (I):
in the formula (I), R1And R2Is hydrogen, optionally substituted C1-20Straight or branched alkyl, optionally substituted C2-20Straight or branched alkenyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Cycloalkyl or optionally substituted C6-20And (4) an aryl group.
In the above technical scheme, in the formula (I), R1And R2Preferably hydrogen, optionally substituted C2-10Straight or branched alkyl, optionally substituted C2-10Straight or branched alkenyl.
In the above technical scheme, the amount of water is as follows: the mass fraction of the water is 0.01-99.99%, preferably 1-90%, more preferably 10-60% of the total mass of the water and the raw material having the structural formula (I).
In the above technical scheme, the catalyst is a molecular sieve, and the molecular sieve is selected from at least one of a ZSM type molecular sieve, a Y type molecular sieve, a Beta type molecular sieve, an L type molecular sieve or an MCM type molecular sieve.
In the above technical scheme, the molecular sieve is preferably a molecular sieve composition, and comprises the following components in parts by weight:
a) 20-80 parts of the molecular sieve;
b) 20-80 parts of a binder.
In the technical scheme, the molecular sieve is at least one selected from ZSM-5, ZSM-11, ZSM-23, ZSM-38, Y, Beta, MCM-22 or MCM-41 molecular sieve; preferably at least one of ZSM-5, Y, Beta or MCM-41 molecular sieves.
In the above technical scheme, the ZSM type molecular sieve has a Si/Al molar ratio SiO2/Al2O310-500 parts; preferably SiO2/Al2O3＝15～100。
In the technical scheme, the Si/Al molar ratio SiO of the Y-type molecular sieve2/Al2O32-70 percent; preferably SiO2/Al2O3＝3～50。
In the technical scheme, the Beta type molecular sieve has the Si/Al molar ratio SiO2/Al2O310-150; preferably SiO2/Al2O3＝15～65。
In the technical scheme, the MCM molecular sieve has the Si/Al molar ratio SiO2/Al2O320-250 parts of; preferably SiO2/Al2O3＝40～150。
In the technical scheme, the molar ratio of silicon to aluminum of the L-type molecular sieve SiO2/Al2O3＝5～100, preferably SiO2/Al2O3＝6～35。
In the above technical scheme, the binder is selected from at least one of silica sol, pseudo-boehmite, alumina, kaolin, montmorillonite or bentonite.
In the above technical scheme, the aromatization reaction conditions comprise: the reaction temperature is 300-800 ℃, and preferably 300-650 ℃; the hydrogen pressure is 0.1-5 MPa, preferably 0.5-4 MPa in gauge pressure; the weight airspeed of the raw material is 0.3-10 hours-1(ii) a Preferably 0.5 to 5 hours-1。
In the above solution, the feedstock is derived from biomass material. Examples of the biomass material include those conventionally used in the art for aromatic hydrocarbon production, and specific examples thereof include xylitol, glucose, cellobiose, cellulose, hemicellulose, lignin, and the like. These biomass materials may be used alone or in combination of two or more.
In the above-described embodiments, specific examples of the biomass material include paper sludge, waste paper, bagasse, glucose, wood, corncobs, cornstalks, and straw stalks. These biomass materials may be used alone or in combination of two or more. Here, the biomass material typically has a cellulose content of 30 to 99%, a hemicellulose content of 0 to 50% and a lignin content of 0 or 1 to 40% in weight percent.
In the above technical scheme, the method further comprises the step of catalytically converting the biomass material to obtain the raw material.
The molecular sieve compositions described in the process of the invention can be used as such or can be prepared according to methods known in the art. Specifically, examples of the method for producing the molecular sieve composition include the following methods: mixing and kneading a molecular sieve, a binder, an extrusion aid, a pore-expanding agent and water which are used as required into a mixture, extruding the mixture into strips, forming the strips, drying the strips at 100-200 ℃ for 1-24 hours, and roasting the strips at 400-700 ℃ for 1-10 hours. Examples of the extrusion aid include sesbania powder, polyethylene glycol, sodium carboxymethylcellulose, and the like which are conventionally used in the art; examples of the pore-expanding agent include those conventionally used in the art, such as citric acid, oxalic acid, and ethylenediaminetetraacetic acid. Generally, the extrusion aid and pore-expanding agent are added in a total amount of no more than 10 wt% of the total weight of the mixture. If necessary, an acid may be added during molding. Examples of the acid include inorganic acids, acetic acid, and aqueous solutions thereof, and particularly aqueous solutions of nitric acid, sulfuric acid, and phosphoric acid. Generally, the aqueous acid solution is added in an amount of 50 to 90 wt% based on the total weight of the mixture.
As an embodiment of the invention, the tetrahydrofurans are derived from biomass material. For example, 2-Methyltetrahydrofuran can be obtained by hydrolysis of Cellulose to obtain Levulinic Acid, followed by Hydrocyclization to obtain 2-Methyltetrahydrofuran (Efficient Conversion of Cellulose to leutinic Acid by hydro-thermal treatment Using Zirconium Dioxide a recycled solvent Catalyst, Ind. Eng. chem. Res., 53(49), pp 18796-18805; Production of leutinic Acid by hydro-thermal synthesis with aqueous phase dehydration with Solid Acid Catalyst, Energy Environ. Sci.,2012,5, 7559-17474; dilution of Hydrogen-Derived reaction of simple reaction 2-moisture reaction 1759, mS 1754). Or can be obtained by hydrolyzing to obtain gamma-valerolactone and then hydrogenating. (Gamma-valerolactone preparation direct conversion of cellulose to free lactic acid and gamma-valerolactone using soluble catalysts, Catal. Sci. Technol.,2013,3,927-
Hydrogen furan Solvent-free γ -valerolactone hydrogenation to 2-methyl tetrahydrofuran purified by Ru/C, Green chem.,2014,16, 1358-.
The contacting step in the process of the present invention may be carried out in one or more reactors. Examples of the reactor include a bed reactor, particularly a fixed bed reactor, a fluidized bed reactor, an ebullating bed reactor, or a combination thereof. In this case, the operation mode of the reactor may be either a batch mode or a continuous mode, and is not particularly limited.
Aromatic hydrocarbons were produced as products according to the aforementioned aromatization process. Generally speaking, the aromatic hydrocarbon product contains more than 60% of BTX aromatic hydrocarbon by weight percentage, in particular, the benzene content is 5.0-10.0%, the toluene content is 30.0-40.0%, the xylene content is 28.0-40.0%, and the rest is non-aromatic hydrocarbon and heavy aromatic hydrocarbon. The heavy aromatic hydrocarbon refers to an aromatic hydrocarbon having nine or more carbon atoms.
After the aromatic hydrocarbons are produced as a product according to the aforementioned aromatization process of the present invention, para-xylene can be separated from the aromatic hydrocarbon product by separation. In view of this, the present invention also relates to a process for producing para-xylene, which comprises the step of producing aromatic hydrocarbons according to the aromatization process of the present invention; and a step of separating paraxylene from the aromatic hydrocarbon.
As an embodiment of the present invention, there is no particular limitation on the method for separating paraxylene from the aromatic hydrocarbon, and those conventionally known in the art can be directly applied.
In one embodiment of the present invention, terephthalic acid can be produced from the paraxylene produced in the above-described manner in the present invention. In view of this, the present invention also relates to a process for producing terephthalic acid, which comprises the steps of producing paraxylene according to the aforementioned process for producing paraxylene of the present invention; and a step of converting p-xylene into terephthalic acid.
As an embodiment of the present invention, there is no particular limitation on the method for converting p-xylene into terephthalic acid, and those conventionally known in the art can be directly applied.
To describe the results of the present invention, in the context of the present specification, T60 was used as an evaluation index. The T60 index refers to the reaction time at which the selectivity to BTX aromatics decreases to 60% in the final product as the reaction proceeds. For example, when T60 is 10, it is said that after 10 hours of reaction, the selectivity of BTX aromatics in the product decreases to 60%; when T60 was 1000, it was shown that the selectivity to BTX aromatics in the product dropped to 60% after 1000 hours of reaction. The larger the value of index T60, the better the carbon deposition resistance of the catalyst and the longer the service time.
The method of the invention has good effect on prolonging the service life of the aromatization catalyst, and solves the problems that the aromatization catalyst is easy to inactivate and needs to be regenerated frequently in the process of preparing aromatic hydrocarbon from biomass. By adopting the method, the aromatization reaction of the raw material with the structural formula (I) is carried out in the presence of water, and the water reacts with carbon deposition in the catalyst to form CO under the aromatization condition, so that the carbon deposition is removed, the aromatization activity of the catalyst is recovered, the service life of the catalyst is further prolonged, the regeneration frequency is reduced, the conversion rate of the raw material can reach 99 percent to the maximum, the T60 of aromatic hydrocarbon can reach 1356 hours, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE ]
Weighing 100 g of corn straw, placing the corn straw in a pressure kettle, adding 700 g of water, adding 5mol/L sulfuric acid solution with the mass of 7% of water, heating to 180 ℃ for reaction for 45 minutes, cooling, filtering the cooled reaction solution to obtain a filter cake and filtrate, wherein the filtrate is cellulose hydrolysate, and after the reaction is finished, identifying the reaction result by mass spectrometry that the main product is levulinic acid and the yield of the levulinic acid is 34 g. The obtained levulinic acid is in Cu/SiO of a fixed bed reactor2The space velocity is 0.6h at the pressure of 3MPa at 250 ℃ on the catalyst-1Hydrogenation under the conditions gave 2-methyltetrahydrofuran in a yield of 91%.
Weighing 35 g of ZSM-5 with the silica-alumina ratio of 25 and 35 g of gamma-alumina, mixing, adding 2.7 g of sesbania powder, and uniformly mixing. Then adding 48 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C1.
Evaluation of catalyst Activity in immobilizationThe reaction is carried out on a bed, and the reaction conditions are as follows: the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran, and the weight space velocity is 1.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was completed, the conversion of 2-methyltetrahydrofuran was 93%, the selectivity for BTX was 85%, and T60 was 85 hours.
[ example 1 ]
Weighing 100 g of corn straw, placing the corn straw in a pressure kettle, adding 700 g of water, adding 5mol/L sulfuric acid solution with the mass of 7% of water, heating to 180 ℃ for reaction for 45 minutes, cooling, filtering the cooled reaction solution to obtain a filter cake and filtrate, wherein the filtrate is cellulose hydrolysate, and after the reaction is finished, identifying the reaction result by mass spectrometry that the main product is levulinic acid and the yield of the levulinic acid is 34 g. The obtained levulinic acid is in Cu/SiO of a fixed bed reactor2The space velocity is 0.6h at the pressure of 3MPa at 250 ℃ on the catalyst-1Hydrogenation under the conditions gave 2-methyltetrahydrofuran in a yield of 91%.
Weighing 35 g of ZSM-5 with the silica-alumina ratio of 25 and 35 g of gamma-alumina, mixing, adding 2.7 g of sesbania powder, and uniformly mixing. Then adding 48 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C1.
The catalyst activity evaluation was carried out on a fixed bed, and the reaction conditions: the mass of the catalyst is 3 g, the reaction substrates are 2-methyltetrahydrofuran and water (60: 40), and the weight space velocity is 1.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was completed, the conversion of 2-methyltetrahydrofuran was 92% and T60 was 1073 hours.
[ example 2 ]
Weighing 35 g of ZSM-5 with the silica-alumina ratio of 50 and 35 g of pseudo-boehmite, mixing, adding 2.7 g of sesbania powder, and uniformly mixing. Then adding 48 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C2.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is tetrahydrofuran and water (30: 70), and the weight space velocity is 2.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was complete, the tetrahydrofuran conversion was 95% and T60 was 1189 hours.
[ example 3 ]
Weighing 60 g of corn straw, placing the corn straw in a pressure kettle, adding 700 g of water, adding 5mol/L sulfuric acid solution with the mass of 7% of water, heating to 180 ℃ for reaction for 45 minutes, cooling, filtering the cooled reaction liquid to obtain a filter cake and filtrate, wherein the filtrate is cellulose hydrolysate, and after the reaction is finished, identifying the reaction result by mass spectrometry that the main product is levulinic acid and the production amount of the levulinic acid is 18 g. The resulting levulinic acid was Cu/SiO in a fixed bed at 20% metal loading2Hydrogenation is carried out at 220 ℃ and under the pressure of 3MPa to obtain the 2-methyltetrahydrofuran, the conversion rate is 99 percent, and the product yield is 93 percent.
Weighing 35 g of ZSM-5 with the silica-alumina ratio of 150 and 35 g of pseudo-boehmite, mixing, adding 2.7 g of sesbania powder, and uniformly mixing. Then adding 48 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C3.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (60: 40), and the weight space velocity is 0.4 h-1Hydrogen pressure 3.0MPa, flow 50ml min-1At a temperature of 500 ℃. After the reaction was complete, the 2-methyltetrahydrofuran conversion was 99% and T60 was 1356 hours.
[ example 4 ]
80 g of ZSM-5 with the silica-alumina ratio of 500 is weighed and mixed with 20 g of pseudo-boehmite, 3.9 g of sesbania powder is added, and the mixture is mixed evenly. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C4.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is tetrahydrofuran and water (20: 80), and the weight space velocity is 5.0 h-1Hydrogen pressure 2.0MPa, flow 30ml min-1And the temperature is 380 ℃. After the reaction was complete, the tetrahydrofuran conversion was 96% and T60 was 940 hours.
[ example 5 ]
80 g of ZSM-38 with the silica-alumina ratio of 150 is weighed and mixed with 20 g of silica sol, 3.9 g of sesbania powder is added and mixed evenly. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C5.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (99: 1) and the weight space velocity is 2.5 hours-1Hydrogen pressure 1.0MPa, flow 20ml min-1The temperature is 480 ℃. After the reaction was complete, the conversion of 2-methyltetrahydrofuran was 95% and T60 was 1060 hours.
[ example 6 ]
80 g of ZSM-11 with the silica-alumina ratio of 150 is weighed and mixed with 20 g of silica sol, 3.9 g of sodium carboxymethylcellulose is added and mixed evenly. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C6.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (90: 10), and the weight space velocity is 1.5 hours-1Hydrogen pressure 1.0MPa, flow 50ml min-1And a temperature of 420 ℃. After the reaction was completed, the conversion of 2-methyltetrahydrofuran was 95% and T60 was 1320 hours.
[ example 7 ]
70 g of ZSM-11 with the silicon-aluminum ratio of 100 is weighed and mixed with 30 g of kaolin, 3.9 g of sesbania powder is added and mixed evenly. Then adding 68.6 g of phosphoric acid aqueous solution with the phosphoric acid mass percentage content of 5.5 percent, kneading and molding, and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C6.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (20: 80), and the weight space velocity is 2.5 hours-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 550 ℃. After the reaction was complete, the 2-methyltetrahydrofuran conversion was 88% and T60 was 1250 hours.
[ example 8 ]
50 g of ZSM-23 with the silica-alumina ratio of 100 is weighed and mixed with 50 g of alumina, 3.9 g of sesbania powder is added and mixed evenly. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C6.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (60: 40), and the weight space velocity is 3.0 h-1Hydrogen pressure 0.5MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was completed, the conversion of 2-methyltetrahydrofuran was 87%, and T60 was 1086 hours.
[ example 9 ]
Weighing 35 g of ZSM-5 with the silica-alumina ratio of 100 and 35 g of gamma-alumina, mixing, adding 2.7 g of sesbania powder, and mixing uniformly. Then adding 48 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C9.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 3-methyltetrahydrofuran + water (10: 90), and the weight space velocity is 3.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was completed, the conversion of 3-methyltetrahydrofuran was 94% and T60 was 1050 hours.
[ example 10 ]
Weighing 35 g of Y molecular sieve with the silicon-aluminum ratio of 6, mixing with 35 g of gamma-alumina, adding 2.7 g of sodium carboxymethylcellulose, and uniformly mixing. Then adding 48 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C10.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (50: 50), and the weight space velocity is 1.8 hours-1Hydrogen pressure 1.0MPa, flow 50ml min-1And a temperature of 420 ℃. After the reaction was completed, the conversion of 2-methyltetrahydrofuran was 92% and T60 was 1182 hours.
[ example 11 ]
60 g of Y molecular sieve with the silicon-aluminum ratio of 8 is weighed and mixed with 40 g of gamma-alumina, 3.9 g of sesbania powder is added, and the mixture is uniformly mixed. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C11.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 3-methyltetrahydrofuran + water (50: 50), and the weight space velocity is 2.2 hours-1Hydrogen pressure 1.0MPa, flow 50ml min-1The temperature is 480 ℃. After the reaction was completed, the conversion of 3-methyltetrahydrofuran was 90% and T60 was 1182 hours.
[ example 12 ]
Weighing 70 g of Y molecular sieve with the silicon-aluminum ratio of 8 and 30 g of pseudo-boehmite, mixing, adding 3.9 g of sesbania powder, and uniformly mixing. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C12.
The evaluation of the catalyst activity was carried out on a fixed bed under reaction conditions of 3 g of catalyst mass and 2, 5-dimethyltetrahydro-base as reaction substrateFuran + water (50: 50), weight space velocity 2.0 hours-1Hydrogen pressure 3.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was completed, the conversion of 2, 5-dimethyltetrahydrofuran was 91% and T60 was 1283 hours.
[ example 13 ]
Weighing 80 g of Y molecular sieve with the silica-alumina ratio of 8, mixing with 20 g of pseudo-boehmite, adding 3.9 g of sesbania powder, and uniformly mixing. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C13.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2, 5-dimethyltetrahydrofuran + water (50: 50), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 350 ℃. After the reaction was complete, the conversion of 2, 5-dimethyltetrahydrofuran was 88% and T60 was 1084 hours.
[ example 14 ]
Weighing 50 g of Beta molecular sieve with the silica-alumina ratio of 30 and 50 g of pseudo-boehmite, mixing, adding 3.9 g of sesbania powder, and uniformly mixing. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C15.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2, 4-dimethyltetrahydrofuran + water (50: 50), and the weight space velocity is 10.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was completed, the conversion of 2, 4-dimethyltetrahydrofuran was 95%, and T60 was 990 hours.
[ example 15 ]
Weighing 60 g of Beta molecular sieve with the silicon-aluminum ratio of 50 and 40 g of pseudo-boehmite, mixing, adding 3.9 g of sesbania powder, and uniformly mixing. Then adding 68.6 g of acetic acid aqueous solution with the mass percentage of acetic acid of 5.5 percent, kneading and molding, and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C15.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2, 3-dimethyltetrahydrofuran + water (80: 20), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 600 ℃. After the reaction was completed, the conversion of 2, 3-dimethyltetrahydrofuran was 97%, and T60 was 1092 hours.
[ example 16 ]
Weighing 70 g of Beta molecular sieve with the silicon-aluminum ratio of 100 and 30 g of pseudo-boehmite, mixing, adding 3.9 g of sesbania powder, and uniformly mixing. Then adding 68.6 g of acetic acid aqueous solution with the mass percentage of acetic acid of 5.5 percent, kneading and molding, and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C16.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2, 3-dimethyltetrahydrofuran + water (80: 20), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was completed, the conversion of 2, 3-dimethyltetrahydrofuran was 98%, and T60 was 991 hours.
[ example 17 ]
50 g of MCM-41 with the silica-alumina ratio of 20 is weighed and mixed with 50 g of pseudo-boehmite, 3.9 g of sesbania powder is added, and the mixture is mixed evenly. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C17.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2, 3-dimethyltetrahydrofuran + water (0.1: 99.9) and the weight space velocity is 0.8 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 320 ℃. After the reaction was completed, the conversion of 2, 3-dimethyltetrahydrofuran was 85% and T60 was 982 hours.
[ example 18 ]
50 g of MCM-22 with the silica-alumina ratio of 50 is weighed and mixed with 50 g of pseudo-boehmite, 3.9 g of sesbania powder is added, and the mixture is mixed evenly. Then adding 68.6 g of nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. The obtained catalyst precursor is dried for 8 hours at 120 ℃ and calcined for 2 hours at 500 ℃ to obtain the molecular sieve catalyst C18.
The evaluation of the catalyst activity is carried out on a fixed bed under the reaction conditions that the mass of the catalyst is 3 g, the reaction substrate is 2-methyltetrahydrofuran + water (80: 20), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was completed, the conversion of 2-methyltetrahydrofuran was 91% and T60 was 1088 hours.
TABLE 1
Claims (14)
1. A process for producing aromatic hydrocarbons by aromatization comprising the step of contacting a feedstock with a catalyst in the presence of water under aromatization reaction conditions to produce aromatic hydrocarbons; wherein the starting material has the structural formula (I):
in the formula (I), R1And R2Is hydrogen, C1-20Straight or branched alkyl, C2-20Straight-chain or branched alkenyl, C2-20Straight-chain or branched alkynyl, C3-20Cycloalkyl or C6-20An aryl group;
wherein the water is used in an amount of: the mass fraction of the water accounts for 10-90% of the total mass of the water and the raw material with the structural formula (I);
the catalyst is a molecular sieve, and the molecular sieve is selected from at least one of a ZSM type molecular sieve, a Y type molecular sieve, a Beta type molecular sieve, an L type molecular sieve or an MCM type molecular sieve;
the aromatization reaction conditions comprise: reaction ofThe temperature is 300-800 ℃, the hydrogen pressure is 0.1-5 MPa in terms of gauge pressure, and the weight airspeed of the raw material is 0.3-10 hours-1。
2. The aromatization process for producing aromatic hydrocarbons according to claim 1 characterized in that in the formula (I), R1And R2Is hydrogen, C2-10Straight or branched alkyl, C2-10Straight or branched alkenyl.
3. The aromatization process for producing aromatics according to claim 1 characterized in that the amount of water used is: the mass fraction of the water accounts for 10-60% of the total mass of the water and the raw material with the structural formula (I).
4. The aromatization process for producing aromatics according to claim 1 characterized in that the molecular sieve is a molecular sieve composition comprising the following components in parts by weight:
a) 20-80 parts of the molecular sieve;
b) 20-80 parts of a binder.
5. The aromatization process for producing aromatics according to claim 1 or 4, characterized in that the molecular sieve is selected from at least one of the ZSM-5, ZSM-11, ZSM-23, ZSM-38, Y, Beta, MCM-22 or MCM-41 molecular sieves.
6. The aromatization process for producing aromatics according to claim 1, characterized in that the molecular sieve is selected from at least one of ZSM-5, Y, Beta or MCM-41 molecular sieves.
7. The aromatization process for producing aromatics according to claim 1, characterized in that the ZSM-type molecular sieve has a silica-alumina molar ratio of SiO2/Al2O310-500 parts; Si/Al molar ratio SiO of Y-type molecular sieve2/Al2O32-70 percent; silicon to aluminum molar ratio SiO of Beta type molecular sieve2/Al2O310-150; silicon-aluminum molar ratio SiO of MCM type molecular sieve2/Al2O320-250 parts of; Si/Al molar ratio SiO of L-type molecular sieve2/Al2O3＝5～100。
8. The aromatization process for producing aromatics according to claim 7 characterized in that the ZSM-type molecular sieve has a silica to alumina molar ratio of SiO2/Al2O315-100 parts; Si/Al molar ratio SiO of Y-type molecular sieve2/Al2O33-50 parts of ═ a; silicon to aluminum molar ratio SiO of Beta type molecular sieve2/Al2O315-65; silicon-aluminum molar ratio SiO of MCM type molecular sieve2/Al2O340-150; Si/Al molar ratio SiO of L-type molecular sieve2/Al2O3＝6～35。
9. The aromatization process for producing aromatics according to claim 4 characterized in that the binder is selected from at least one of silica sol, pseudo-boehmite, alumina, kaolin, montmorillonite or bentonite.
10. The aromatization process for producing aromatics according to claim 1 characterized in that the feedstock is derived from a biomass material.
11. The aromatization process for producing aromatics according to claim 1 characterized in that the feedstock is derived from at least one of xylitol, glucose, cellobiose, cellulose, hemicellulose and lignin; or derived from at least one of paper sludge, waste paper, bagasse, wood, corn cobs, corn stover, and rice straw.
12. The aromatization process for producing aromatics according to claim 1 characterized in that said process further comprises the step of subjecting a biomass material to catalytic conversion to obtain said feedstock.
13. A method for producing paraxylene, comprising the steps of:
a step of producing aromatic hydrocarbons according to the method of any one of claims 1 to 12; and
a step of separating p-xylene from the aromatic hydrocarbon.
14. A process for producing terephthalic acid, comprising the steps of:
a step of producing paraxylene according to the method of claim 13; and
a step of converting p-xylene into terephthalic acid.
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|---|---|---|---|---|
| US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
| US5981819A (en) * | 1996-11-26 | 1999-11-09 | Metallgesellschaft Aktiengesellschaft | Process of generating C3 - and C4 -olefins from a feed mixture containing C4 to C7 olefins |
| CN103664482A (en) * | 2013-12-03 | 2014-03-26 | 浙江大学 | Reaction technology for converting oxygen-containing compound into aromatic hydrocarbons by using moving bed process |
| CN105498827A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for efficient preparation of biomass based aromatic hydrocarbon |
| CN105498828A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparation of light aromatic hydrocarbon by furan compound aromatization |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
| US5981819A (en) * | 1996-11-26 | 1999-11-09 | Metallgesellschaft Aktiengesellschaft | Process of generating C3 - and C4 -olefins from a feed mixture containing C4 to C7 olefins |
| CN103664482A (en) * | 2013-12-03 | 2014-03-26 | 浙江大学 | Reaction technology for converting oxygen-containing compound into aromatic hydrocarbons by using moving bed process |
| CN105498827A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for efficient preparation of biomass based aromatic hydrocarbon |
| CN105498828A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparation of light aromatic hydrocarbon by furan compound aromatization |
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