CN107586238B - Method for aromatizing lactone compounds - Google Patents
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Abstract
The invention relates to a method for aromatizing lactone compounds, which comprises the step of contacting the lactone compounds with a catalyst under aromatization reaction conditions to produce aromatic hydrocarbons in the presence of water; wherein the lactone compound has a structural formula (I):
in the formula (I), R1Selected from optionally substituted C1‑20Straight or branched alkylene, optionally substituted C2‑20Straight or branched alkenylene, optionally substituted C2‑20Straight or branched alkynylene, optionally substituted C3‑20Cycloalkylene and optionally substituted C6‑20An arylene group; r2Selected from hydrogen, optionally substituted C1‑20Straight or branched chain alkyl and carboxyl; the catalyst is at least one of Lewis acid supported solid super acid, inorganic metal salt/Lewis acid composite solid super acid or sulfated metal oxide solid super acid.
Description
Technical Field
The invention relates to a method for aromatizing lactone compounds, in particular to a method for preparing 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).
The biomass lactone compound is typically valerolactone, and can be obtained by hydrolyzing and deoxidizing cellulose. Gamma valerolactone has been listed as one of the biomass platform compounds and can be converted to gasoline, additives and other chemicals by catalytic means. For example, the use of H over an acidic carrier-supported noble metal catalyst2Reducing to obtain valeric acid. The valeric acid can generate decarboxylation coupling reaction through the catalysis of the mixture of cerium oxide and zirconium oxide to generate 5-nonanone, and the gasoline component can be obtained through hydrogenation reduction. Using Pd/NbO2Catalyst, hydrogenation of 50% gamma valerolactone in water at 325 ℃, 3.5MPa, gave a yield of 92% valeric acid (j.c. serrano-Ruiz, d.wang, j.a. dumesic, Catalytic upgrading of levulinic to 5-nonanone, Green Chemistry 2010,12, 574-one 577.).
The inventor of the present application has applied for a patent (CN201510345799.2) on the aromatization of lactone compounds as platform compounds to prepare BTX aromatic hydrocarbons. However, in the subsequent development process, the lactone compound has a C4 olefin intermediate in the conversion process, which is easy to form polyolefin and carbon deposition, coke on the catalyst, and cause the catalyst to be deactivated and short in 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 lactone compounds, so that carbon deposition is generated to cause the inactivation of a catalyst, and provides a novel method for aromatizing lactone compounds. 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 method for aromatizing a lactone compound comprises the steps of contacting the lactone compound with a catalyst under aromatization reaction conditions in the presence of water to produce aromatic hydrocarbons; wherein the lactone compound has a structural formula (I):
in the formula (I), R1Selected from optionally substituted C1-20Straight or branched alkylene, optionally substituted C2-20Straight or branched alkenylene, optionally substituted C2-20Straight or branched alkynylene, optionally substituted C3-20Cycloalkylene and optionally substituted C6-20An arylene group; r2Selected from hydrogen, optionally substituted C1-20Straight or branched chain alkyl and carboxyl;
the catalyst is at least one of Lewis acid supported solid super acid, inorganic metal salt/Lewis acid composite solid super acid or sulfated metal oxide solid super acid.
In the technical proposal, the device comprises a base,in the formula (I), the R1Selected from optionally substituted C2-10Straight or branched alkylene and optionally substituted C2-10Straight-chain or branched alkenylene, preferably C2-5Straight-chain or branched alkylene, and more preferably 1, 2-ethylene.
In the above technical solution, in the formula (I), R is2Selected from hydrogen and optionally substituted C1-10Straight or branched alkyl, preferably selected from hydrogen and C1-4Straight or branched chain alkyl.
In the above-mentioned embodiment, the compound having a lactone group includes, in particular, γ -valerolactone.
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 solid super acid may be used alone, or two or more kinds may be used in combination. These solid superacids can be used as such or can be produced according to methods known in the art.
In the above technical scheme, the lewis acid supported solid super acid comprises a carrier and lewis acid supported on the carrier. Examples of the carrier include solid oxides of group IIIA elements and solid oxides of group IVA elements in the periodic Table of elements, particularly SiO2、B2O3And Al2O3. These carriers may be used alone or in combination of two or more. Examples of the Lewis acid include a halide of a group VB element, a halide of a group IIIA element and a halide of a group VA element of the periodic Table of the elements, particularly a halide of a group VB element and a halide of a group VA element of the periodic Table of the elements, more particularly PF3、AsF3、SbF3、BiF3、SbF5、TaF3、VF3And NbF3. Here, as the halide, fluoride is preferable. These Lewis acids may be used alone or in combination of two or more. More specifically, asExamples of the Lewis acid-supported solid superacid include SbF5/SiO2-Al2O3、PF3/Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-B2O3And NbF3/Al2O3-B2O3. These lewis acid-supported solid super acids may be used alone or in combination of two or more.
In the technical scheme, in the lewis acid supported solid super acid, the supported amount of the lewis acid is 1 to 30wt%, preferably 1 to 15wt%, relative to the weight of the carrier.
In the above technical scheme, the inorganic metal salt/lewis acid composite solid super acid is a composite composed of an inorganic metal salt and lewis acid. Examples of the inorganic metal salt include inorganic acid salts of group IB metal elements, inorganic acid salts of group IIB metal elements, inorganic acid salts of group VII metal elements, and inorganic acid salts of group VIII metal elements of the periodic table. Here, the inorganic acid salt includes, in particular, a hydrohalide salt, particularly a hydrochloride salt. These inorganic metal salts may be used alone or in combination of two or more. Examples of the Lewis acid include a halide of a group VB element, a halide of a group IIIA element and a halide of a group VA element of the periodic Table of the elements, particularly a halide of a group IIIA element of the periodic Table of the elements. Here, as the halide, a chloride is preferable. These Lewis acids may be used alone or in combination of two or more. The inorganic metal salt/Lewis acid composite solid super acid includes, in particular, AlCl3-CuCl2. The inorganic metal salt/Lewis acid composite solid superacid can be used alone or in combinationUsed in combination of two or more.
In the technical scheme, in the inorganic metal salt/lewis acid composite solid super acid, the weight ratio of the inorganic metal salt to the lewis acid is 1-30: 100, preferably 1 to 15: 100.
in the above-described embodiment, in the sulfated metal oxide type solid super acid, examples of the metal oxide include an oxide of a metal element of group IVB of the periodic table (hereinafter referred to as oxide a), and an oxide obtained by modifying the oxide a with a modifying element such as a metal element of group IIIA, a metal element of group VIIB, a noble metal element of group VIII, a base metal element of group VIII, a metal element of group VIB, or a lanthanoid metal element of the periodic table (hereinafter referred to as oxide B). These metal oxides may be used alone or in combination of two or more. These modifying elements may be used alone or in combination of two or more. Specific examples of the oxide A include ZrO2、TiO2Or a combination thereof. Specific examples of the modifier element include Fe, Pt, Re, Al, W, Cr, Mo, Mn, and a combination thereof. In the oxide B, the metal elements in group IIIA of the periodic table are generally present in the form of oxides, the metal elements in group VIIB are generally present in the form of oxides, the noble metal elements in group VIII are generally present in the form of elemental metals, the base metal elements in group VIII are generally present in the form of oxides, the metal elements in group VIB are generally present in the form of oxides, and the lanthanide metal elements are generally present in the form of oxides. As the sulfated metal oxide type solid super acid, SO may be mentioned in particular4 2－/ZrO2、S2O8 2－/ZrO2、SO4 2－/TiO2、SO4 2－/ZrO2-Fe3O4、Pt/SO4 2－/TiO2、SO4 2－/TiO2-ZrO2、SO4 2－/TiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2－/ZrO2-Fe2O3-Cr2O3、SO4 2－/ZrO2-WO3、SO4 2-/TiO2-MoO3And SO4 2－/ZrO2-Fe2O3-MnO2. These sulfated metal oxide type solid superacids described above may be used alone or in combination of two or more.
In the above technical solution, in the oxide B, the weight ratio of the modifying element (in terms of oxide) existing in the form of oxide to the oxide a is generally 0.1 to 25: 100, preferably 0.5 to 10: 100, and the weight ratio of the modifying element (calculated as metal) in the form of metal simple substance to the oxide A is generally 0.1-15: 100, preferably 0.3 to 6: 100.
in the above technical solution, in the sulfated metal oxide type solid super acid, the sulfation rate of the metal oxide is generally 0.5 to 25wt%, preferably 1 to 8 wt%.
In the above-mentioned embodiments, the method for producing the sulfated metal oxide type solid super acid is not particularly limited, and those conventionally known in the art can be used, and specific examples thereof include a precipitation-impregnation method (see, for example, the document "SO" for reference)4 2-/MxOyResearch on the solid super acidic catalyst is advanced and applied in chemical industry, 2014, vol43, 1879-.
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.
According to an embodiment of the present invention, a method for deriving the compound having a lactone group from the biomass material is not particularly limited, and those conventionally known in the art may be used. For example, the derivatization process may, for example, comprise the step of subjecting the biomass material to a catalytic conversion (e.g. hydrolytic deoxygenation) to directly produce the compound having lactone groups (in particular γ -valerolactone) (see, for example, Direct conversion of cellulosic to free lactic acid and gamma-lactonic using solid acids systems, cal. Sci. Technol.,2013,3, 927. alpha. 931; Production of free lactic acid and gamma-lactonic (GVL) from cellulosic use GVL a solvent in biological systems, Energy environ. Sci.,2012,5, 8199. alpha. 8203).
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 method for aromatizing lactone compounds. 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, the C-C bond in the carbon deposit is activated by the super-strong acid site of the catalyst to cause heterolysis under the aromatization condition and in the presence of water, and the C-C bond in the carbon deposit is opened to simultaneously carry out elimination reaction, so that the carbon deposit 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 94 percent at most, the T60 of aromatic hydrocarbon can reach 995 hours, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE ]
Weighing 50 g of bagasse, placing the bagasse into a pressure kettle, adding 500 g of water, adding 5mol/L hydrochloric acid solution with the mass of 5% of the water, heating to 180 ℃ for reaction for 1 hour, cooling, filtering the cooled reaction solution to obtain a filter cake and a filtrate, wherein the filtrate is a cellulose hydrolysate, and after the reaction is finished, identifying the reaction result by mass spectrometry that the main product is levulinic acid and the generation amount of the levulinic acid is 16 g. The levulinic acid obtained is hydrogenated in a fixed bed on RuSn/C with 2 percent of metal loading to obtain gamma-valerolactone, the conversion rate is 99 percent, and the product yield is 98 percent.
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-valerolactone
Weight space velocity of 0.3 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The gamma valerolactone conversion was 99% and T60 was 72 hours.
[ example 1 ]
Weighing 50 g of bagasse, placing the bagasse into a pressure kettle, adding 500 g of water, adding 5mol/L hydrochloric acid solution with the mass of 5% of the water, heating to 180 ℃ for reaction for 1 hour, cooling, filtering the cooled reaction solution to obtain a filter cake and a filtrate, wherein the filtrate is a cellulose hydrolysate, and after the reaction is finished, identifying the reaction result by mass spectrometry that the main product is levulinic acid and the generation amount of the levulinic acid is 16 g. The levulinic acid obtained is hydrogenated in a fixed bed on RuSn/C with 2 percent of metal loading to obtain gamma-valerolactone, the conversion rate is 99 percent, and the product yield is 98 percent.
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-valerolactone
+ water (50: 50) at a weight space velocity of 0.3 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The gamma valerolactone conversion was 98% and T60 was 970 hours.
[ example 2 ]
5 g of S are weighed out and dried at 120 ℃ for 12 hours2O8 2－/ZrO2Catalyst, loading into fixed bed reactor. The reaction substrate is propyl dodecalactone
+ water (50: 50), weight space velocity 1.0 h-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 450 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The conversion of the dodecyl propyl ester was 93% and the T60 was 930 h.
[ example 3 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/TiO2Catalyst, loading into fixed bed reactor. The reaction substrate is propyl caprolactone
+ water (10: 90), weight space velocity 3.0 hours-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. Caprolactone propyl conversion was 85% and T60 was 807 hours.
[ example 4 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2-Fe3O4Catalyst, loading into fixed bed reactor. The reaction substrate is gamma decalactone
+ water (60: 40), weight space velocity 5.0 h-1Hydrogen pressure 1.0MPa, flow 20ml min-1At a temperature of 500 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The conversion of the propyl decalin was 86% and T60 was 810 hours.
[ example 5 ]
5 g of Pt/SO were weighed out and dried at 120 ℃ for 12 hours without water4 2－/TiO2Catalyst, loading into fixed bed reactor. The reaction substrate is propiolactone and water (90: 10), the weight space velocity is 2.0 h-1, the hydrogen pressure is 3.0MPa, and the flow is 20ml min-1And the temperature is 450 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The conversion of heptalactone was 88% and T60 was 820 hours.
[ example 6 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/TiO2-ZrO2Catalyst, loading into fixed bed reactor. The reaction substrate is the propyl octalactone plus water (99: 1), the weight space velocity is 0.8 hour-1Hydrogen pressure 1.0MPa, flow 40mlmin-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The conversion of the propyl octalactone was 94% and the T60 was 995 hours.
[ example 7 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/TiO2-Al2O3Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-butyrolactone + water (99.9: 0.1), and the weight space velocity is 1.0 h-1Hydrogen pressure 1.0MPa, flow 20mlmin-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The gamma-butyrolactone conversion was 81% and T60 was 950 hours.
[ example 8 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2-Fe2O3-Cr2O3Catalyst, loading into fixed bed reactor. The reaction substrate is epsilon-caprolactone + water (95: 5), and the weight space velocity is 2.0 h-1Hydrogen pressure 1.0MPa, flow 50mlmin-1And the temperature is 450 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The conversion of epsilon-caprolactone was 95% and T60 was 905 hours.
[ example 9 ]
5 g of SbF are weighed out and dried at 120 ℃ for 12 hours without water5/SiO2-Al2O3Catalyst, loading into fixed bed reactor. The reaction substrate is delta-valerolactone and water (80: 20), and the weight space velocity is 3.0 h-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The delta-valerolactone conversion was 87% and T60 was 890 hours.
[ example 10 ]
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 solution to obtain a filter cake and a filtrate, wherein the filtrate is a hydrolysis solution of cellulose, and after the reaction is finished, mass spectrometry is adopted to carry out the reactionThe fruit was identified as having a major product of levulinic acid, which was produced in an amount of 18 grams. The resulting levulinic acid was Cu/SiO in a fixed bed at 20% metal loading2The gamma-valerolactone is obtained by hydrogenation, the conversion rate is 99 percent, and the product yield is 98 percent.
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2-/TiO2-WO3Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-valerolactone and water (60: 40), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 20ml min-1At a temperature of 500 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The gamma valerolactone conversion was 86% and T60 was 860 hours.
[ example 11 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2-WO3Catalyst, loading into fixed bed reactor. The reaction substrate is angelica lactone and water (60: 40), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 380 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The angelicin conversion was 92% and T60 was 880 hours.
[ example 12 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2-/TiO2-MoO3Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-valerolactone and water (50: 50), and the weight space velocity is 2.0 hours-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 380 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The conversion rate of gamma-penton was 82% and T60 was 903 hours.
[ example 13 ]
5 g of BiF are weighed, dried at 120 ℃ for 12 hours without water3/Al2O3-B2O3Catalyst is filled into a fixed bed reactor, and reaction substrates are β -propiolactone and water (C)70: 30) weight space velocity of 1.0 hour-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 420 ℃, after the reaction is finished, the qualitative analysis is carried out on the reaction result by adopting a mass spectrum, and the quantitative analysis is carried out on the reaction result by adopting a chromatogram, the conversion rate of the β -propyl lactone is 87 percent, and the T60 is 860 hours.
[ example 14 ]
Weighing 5 g of NbF dried at 120 ℃ for 12 hours3/Al2O3-B2O3Catalyst, loading into fixed bed reactor. The reaction substrate is propyl caprolactone
+ water (85:15), weight space velocity 2.0 hours-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 360 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. Caprolactone propyl conversion was 88% and T60 was 904 hours.
[ example 15 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2-Fe2O3-MnO2Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-butyrolactone + water (95: 5), and the weight space velocity is 2.0 h-1Hydrogen pressure 1.0MPa, flow 20mlmin-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The gamma-butyrolactone conversion was 89%, and T60 was 850 hours.
[ example 16 ]
5 g of SO are weighed out and dried at 120 ℃ for 12 hours without water4 2－/ZrO2-Fe2O3-Cr2O3Catalyst, loading into fixed bed reactor. The reaction substrate is angelica lactone and water (95: 5), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 20mlmin-1And the temperature is 380 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. When in useThe angelica lactone conversion was 92% and T60 was 840 hours.
[ example 17 ]
Weighing 5 g of AlCl which is dried at 120 ℃ for 12 hours to remove water3-CuCl2Catalyst, loading into fixed bed reactor. The reaction substrate is gamma-valerolactone and water (97: 3), and the weight space velocity is 2.5 hours-1Hydrogen pressure 1.0MPa, flow 20ml min-1And the temperature is 400 ℃. After the reaction is finished, the reaction result is qualitatively analyzed by adopting a mass spectrum, and the reaction result is quantitatively analyzed by adopting a chromatogram. The gamma valerolactone conversion was 83% and T60 was 920 hours.
TABLE 1
Claims (14)
1. A method for aromatizing a lactone compound comprises the steps of contacting the lactone compound with a catalyst under aromatization reaction conditions in the presence of water to produce aromatic hydrocarbons; wherein the lactone compound has a structural formula (I):
in the formula (I), R1Is selected from C1-20Straight or branched alkylene and C2-20Straight or branched alkenylene; r2Selected from hydrogen and C1-20A linear or branched alkyl group;
the aromatization reaction conditions comprise: the reaction 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；
The dosage of the water is as follows: 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 selected from at least one of Lewis acid supported solid super acid, inorganic metal salt/Lewis acid composite solid super acid or sulfated metal oxide solid super acid;
wherein the Lewis acid supported solid super acid is selected from SbF5/SiO2-Al2O3、PF3/Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-B2O3And NbF3/Al2O3-B2O3One or more of;
the inorganic metal salt/Lewis acid composite solid super acid is AlCl3-CuCl2；
The sulfated metal oxide type solid super acid is selected from SO4 2－/ZrO2、S2O8 2－/ZrO2、SO4 2－/TiO2、SO4 2－/ZrO2-Fe3O4、Pt/SO4 2－/TiO2、SO4 2－/TiO2-ZrO2、SO4 2－/TiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2－/ZrO2-Fe2O3-Cr2O3、SO4 2－/ZrO2-WO3、SO4 2-/TiO2-MoO3And SO4 2－/ZrO2-Fe2O3-MnO2One or more of (a).
2. The method for aromatization of lactones according to claim 1, characterized in that in formula (I), R is1Is selected from C2-10Straight or branched alkylene and C2-10Straight or branched alkenylene; r2Selected from hydrogen and C1-10Straight or branched chain alkyl.
3. The method for aromatization of lactones according to claim 2, characterized in that in formula (I), R is1Is selected from C2-5A linear or branched alkylene group; r2Selected from hydrogen and C1-4Straight or branched chain alkyl.
4. The method for aromatization of lactones according to claim 2, characterized in that in formula (I), R is1Is a1, 2-ethylene group.
5. The method for aromatizing lactone compounds according to claim 1, wherein 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).
6. The method for aromatization of lactones according to claim 1, characterized in that the supported amount of the Lewis acid in the Lewis acid supported solid super acid is 1-30 wt% relative to the weight of the carrier;
in the inorganic metal salt/Lewis acid composite solid superacid, CuCl2With AlCl3The weight ratio of (A) to (B) is 1-30: 100, respectively;
in the sulfated metal oxide type solid super acid, the sulfation rate of the metal oxide is 0.5-25 wt%.
7. The method for aromatization of lactones according to claim 6, characterized in that the supported amount of Lewis acid in the Lewis acid supported solid superacid is 1-15 wt% relative to the weight of the carrier.
8. The method for aromatization of lactones according to claim 6, characterized in that in the inorganic metal salt/Lewis acid composite solid super acid, CuCl is added2With AlCl3The weight ratio of (A) to (B) is 1-15: 100.
9. the method for aromatizing lactones according to claim 6, wherein the sulfation ratio of the metal oxide in the sulfated metal oxide type solid super acid is 1-8 wt%.
10. The lactone-based aromatization process of claim 1 characterized in that the feedstock is derived from a biomass material.
11. The lactone aromatization process of 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 method of aromatization of lactones according to claim 1, characterized in that it further comprises the step of subjecting 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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