CN107586239B

CN107586239B - Method for synthesizing aromatic hydrocarbon by aromatization

Info

Publication number: CN107586239B
Application number: CN201610538894.9A
Authority: CN
Inventors: 宋奇; 孔德金; 郑均林
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2016-07-08
Filing date: 2016-07-08
Publication date: 2020-03-31
Anticipated expiration: 2036-07-08
Also published as: CN107586239A

Abstract

The invention relates to a method for aromatizing and synthesizing aromatic hydrocarbon, which comprises the steps of contacting raw materials with a catalyst under the aromatization reaction condition in the presence of water to produce aromatic hydrocarbon; wherein the starting material has the structural formula (I):

in the formula (I), R₁Is optionally substituted C_1‑8Straight or branched alkyl, optionally substituted C_2‑8Straight or branched alkenyl; r₂Is hydrogen, optionally substituted C_1‑10A straight chain or branched chain alkyl group, wherein n is a positive integer of 1-6; 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

Method for synthesizing aromatic hydrocarbon by aromatization

Technical Field

The invention relates to a method for synthesizing aromatic hydrocarbon by aromatization, 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).

Levulinic acid (4-oxovaleric acid, levogluconic acid, or pentofuranonic acid) is a short chain non-volatile fatty acid. Levulinic acid is low in toxicity and hygroscopic, almost does not decompose in distillation under normal pressure, contains carbonyl and carboxyl in molecules, is easy to generate a series of chemical reactions such as salt formation, esterification, hydrogenation, condensation, oxidation and halogenation, is an important intermediate for preparing various high-added-value chemical products, and is widely applied to industrial fields such as spices, solvents, oil additives, medicines, plasticizers and the like. The levulinate is a short-chain fatty acid ester which is generally colorless liquid and has a high boiling point, is also an important organic chemical, can be directly used as a spice, a food additive, a gasoline additive, a biological liquid fuel and the like, and can be used in the industries of food, cosmetics, medicines, plastics, transportation and the like.

The method comprises the steps of firstly converting hexa-carbon sugar into levulinic acid and formic acid, then carrying out alkali treatment to form metal salt, and then carrying out electrolytic decarboxylation in an electrolytic cell to obtain methyl ethyl ketone which can be used as a solvent, and the document US20060247444A1 discloses the step of converting levulinic acid into N-alkyl pyrrolidone, wherein the N-alkyl pyrrolidone can be used as a solvent, a surfactant, a dispersing agent and an emulsifying agent, and can be used for maintenance of oil wells and gas wells, synthesis of polymers and medicine.

The inventor of the present application has applied for patent (CN201510345909.5) on the aromatization of levulinic acid compounds as platform compounds to prepare BTX aromatic hydrocarbons. However, in the subsequent development process, the levulinic acid compound has a C4 olefin intermediate in the conversion process, so that polyolefin and carbon deposit are easily formed and coke on the catalyst, so that the catalyst is inactivated and has 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 levulinic acid compounds, so that carbon deposition is generated, and the catalyst is inactivated, and provides a novel aromatization aromatic hydrocarbon synthesis method. 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 synthesizing aromatic hydrocarbon by aromatization comprises the steps of contacting a raw material 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), R₁Is optionally substituted C_1-8Straight or branched alkyl, optionally substituted C_2-8Straight or branched alkenyl; r₂Is hydrogen, optionally substituted C_1-10A straight chain or branched chain alkyl group, wherein n is a positive integer of 1-6;

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 above technical scheme, in the formula (I), R₁Preferably optionally substituted C_1-4Straight or branched chain alkyl, more preferably methyl.

In the above technical scheme, R₂Preferably hydrogen, optionally substituted C_1-5Straight or branched chain alkyl, more preferably hydrogen.

In the above technical solution, n is a positive integer of 1 to 4, and more preferably n is 2.

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, the Lewis acid-supported solid superacid includes, for example, 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, chlorine is preferableAnd (4) melting the mixture. 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. These inorganic metal salt/lewis acid composite solid superacids may be used alone or 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-/M_xO_yResearch 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.

As an embodiment of the present invention, a method for deriving the raw material having the general formula (I) from the biomass material is not particularly limited, and those conventionally known in the art may be employed. For example, the derivatization process may for example comprise the step of subjecting the Biomass material to a catalytic conversion (such as hydrolytic deoxygenation, mineral Acid catalyzed hydrolysis, organic Acid catalyzed hydrolysis, solid Acid catalyzed hydrolysis, molecular sieve catalyzed hydrolysis, supercritical hydrolysis, catalytic partial oxidation or metal chloride catalysis) to produce the feedstock (in particular levulinic Acid) (see for example Direct conversion of cell to free-cell Acid and gamma-solvent Using soluble acids, catalyst. Sci. technique, 2013,3, 927-.

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, 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 catalytic environment of 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 99 percent at most, the T60 of aromatic hydrocarbon can reach 1152 hours, and 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.

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 levulinic acid

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. Levulinic acid conversion was 91% and T60 was 207 hours.

[ example 1 ]

+ water (90/10), weight space velocity 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 levulinic acid conversion was 90% and T60 was 1085 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 acetoacetic acid

+ water (80/20), weight space velocity 1.0 hr^-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 acetoacetic acid conversion was 91% and T60 was 1115 hours.

[ 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 levulinic acid

+ water (50/50), weight space velocity 3.0 hr^-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 levulinic acid conversion was 94% and T60 was 1194 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 ethyl acetoacetate

+ water (60/40), weight space velocity 5.0 hr^-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 ethyl acetoacetate conversion was 99% and T60 was 936 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 methyl levulinate

+ water (99.9/0.1), weight space velocity 2.0 hours^-1Hydrogen pressure 3.0MPa, 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 methyl levulinate was 87% and T60 was 1087 hours.

[ example 6 ]

Weighing 5 g of the powderDrying at 120 deg.C for 12 hr to remove SO₄ ^2－/TiO₂-ZrO₂Catalyst, loading into fixed bed reactor. The reaction substrate is methyl acetylbutyrate

+ water (10/90), weight space velocity 0.8 h^-1Hydrogen pressure 4.0MPa, flow 40ml 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 conversion of methyl acetylbutyrate was 92% and T60 was 1099 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 octyl levulinate

+ water (80/20), weight space velocity 3.0 hr^-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 conversion of octyl acetylacetonate was 92% and T60 was 1047 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 ethyl levulinate

+ water (75/25), weight space velocity 2.0 h^-1Hydrogen pressure 1.0MPa, flow 50ml 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 ethyl levulinate was 87% and T60 was 1076 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 butyl levulinate

+ water (70/30), weight space velocity 3.0 hr^-1Hydrogen pressure 1.0MPa, flow 20ml min^-1And the temperature is 470 ℃. 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 butyl levulinate was 99% and T60 was 1152 hours.

[ example 10 ]

Weighing 60 g of corn straw, placing the corn straw in a pressure kettle, adding 340 g of ethanol, adding 5mol/L sulfuric acid solution with the water mass of 7%, heating to 180 ℃ for reaction for 45 minutes, cooling, filtering the cooled reaction liquid to obtain a filter cake and a filtrate, wherein the filtrate is a hydrolysis liquid of cellulose, and after the reaction is finished, identifying the reaction result by mass spectrometry that a main product is ethyl levulinate and the generation amount of the levulinate group in the product is 18 g.

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 ethyl levulinate

+ water (80/20), weight space velocity 1.0 hr^-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 ethyl levulinate was 93% and T60 was 1127 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 decyl levulinate

+ water (90/10), weight space velocity 1.0 hr^-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. Decyl levulinate conversion was 88%, T60 was 1166 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 methyl levulinate

+ water (95/5), weight space velocity 2.0 h^-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 of methyl levulinate was 98% and T60 was 1181 hours.

[ example 13 ]

5 g of BiF are weighed, dried at 120 ℃ for 12 hours without water₃/Al₂O₃-B₂O₃Catalyst, loading into fixed bed reactor. The reaction substrate is methyl levulinate + water (95/5), and the weight space velocity is 1.0 h^-1Hydrogen pressure 1.0MPa, flow 20ml min^-1And a temperature of 420 ℃. 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 methyl levulinate was 88% and T60 was 1187 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 methyl acetylhexanoate

+ water (99/1) at a weight space velocity of 2.0 hTime of flight^-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. The conversion of methyl acetylhexanoate was 87% and T60 was 947 h.

[ 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 butyl levulinate

+ water (50/50), weight space velocity 2.0 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 conversion of the butyl levulinate was 94% and T60 was 1053 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 butyl levulinate and water (90/10), and the weight space velocity is 1.0 h^-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 of butyl levulinate was 93% and T60 was 938 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 butyl levulinate + water (95/5), and the weight space velocity is 3.5 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. Conversion rate of butyl levulinate is 97%, TAt 60, 995 hours.

TABLE 1

Claims

1. A method for synthesizing aromatic hydrocarbon by aromatization comprises the steps of contacting a raw material 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):

（I）

in the formula (I), R₁Is C_1-8Straight or branched alkyl, C_2-8Straight or branched alkenyl; r₂Is hydrogen, C_1-10A straight chain or branched chain alkyl group, wherein n is a positive integer of 1-6;

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 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 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 isAlCl₃-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;

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。

2. The aromatization synthesis process of aromatic hydrocarbons according to claim 1 characterized in that in formula (I), R₁Is C_1-4A linear or branched alkyl group; r₂Is hydrogen, C_1-5The alkyl group is a straight chain or branched chain alkyl group, and n is a positive integer of 1-4.

3. The aromatization synthesis process of aromatic hydrocarbons according to claim 2 characterized in that in formula (I), R₁Is methyl; r₂Is hydrogen; n = 2.

4. The method for aromatizing synthetic aromatics 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).

5. The aromatization method for synthesizing aromatic hydrocarbons according to claim 1, characterized in that the loading amount of the Lewis acid in the Lewis acid supported solid superacid is 1 to 30wt% 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,

in the sulfated metal oxide type solid super acid, the sulfation rate of the metal oxide is 0.5-25 wt%.

6. The aromatization method for synthesizing aromatic hydrocarbons according to claim 1, characterized in that the loading amount of the Lewis acid in the Lewis acid supported solid superacid is 1-15 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 1-15: 100,

in the sulfated metal oxide type solid super acid, the sulfation rate of the metal oxide is 1-8 wt%.

7. The process for aromatization synthesis of aromatics according to claim 1 characterized in that the feedstock is derived from a biomass material.

8. The method of aromatizing synthetic 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.

9. The aromatization process for synthesizing aromatic hydrocarbons 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.

10. 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 9; and

a step of separating p-xylene from the aromatic hydrocarbon.

11. A process for producing terephthalic acid, comprising the steps of:

a step of producing paraxylene according to the method of claim 10; and

a step of converting p-xylene into terephthalic acid.