CN107721794B - Aromatization process - Google Patents
Aromatization process Download PDFInfo
- Publication number
- CN107721794B CN107721794B CN201610649375.XA CN201610649375A CN107721794B CN 107721794 B CN107721794 B CN 107721794B CN 201610649375 A CN201610649375 A CN 201610649375A CN 107721794 B CN107721794 B CN 107721794B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- type molecular
- process according
- aromatization
- straight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
Abstract
The invention relates to an aromatization method, which comprises the step of adding an alcohol compound R into an alcohol compound3A step of contacting a raw material with a catalyst in the presence of OH under aromatization reaction conditions to produce aromatic hydrocarbons; wherein the starting material has the structural formula (I):
in the formula (I), R1Is optionally substituted C1‑8Straight or branched alkyl, optionally substituted C2‑8Straight or branched alkenyl; r2Is hydrogen, optionally substituted C1‑10A straight chain or branched chain alkyl group, wherein n is a positive integer of 1-6; the catalyst is a molecular sieve composition comprising the following components: a) 20-80 parts by weight of a molecular sieve; the molecular sieve is selected from at least one of ZSM type molecular sieve, Y type molecular sieve, Beta type molecular sieve, L type molecular sieve or MCM type molecular sieve; b) 20-80 parts by weight of a binder; c) 0.01-10 parts of an auxiliary agent.
Description
Technical Field
The present invention relates to a process for aromatization, in particular a process for producing BTX aromatics. 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 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: an aromatization method comprising adding an alcohol compound R into an alcohol compound3A step of contacting a raw material with a catalyst in the presence of OH under aromatization reaction conditions to produce aromatic hydrocarbons; wherein the starting material has the structural formula (I):
in the formula (I), R1Is optionally substituted C1-8Straight or branched alkyl, optionally substituted C2-8Straight or branched alkenyl; r2Is hydrogen, optionally substituted C1-10A straight chain or branched chain alkyl group, wherein n is a positive integer of 1-6;
R3is optionally substituted C1-20Straight or branched alkyl, optionally substituted C2-20Straight or branched alkenyl, optionally substituted C3-20A straight or branched chain cycloalkyl group;
the catalyst is a molecular sieve composition comprising the following components:
a) 20-80 parts by weight of a molecular sieve; the molecular sieve is selected from at least one of ZSM type molecular sieve, Y type molecular sieve, Beta type molecular sieve, L type molecular sieve or MCM type molecular sieve;
b) 20-80 parts by weight of a binder;
c) 0.01-10 parts by weight of an auxiliary agent; the auxiliary agent is at least one selected from Na, Ca, K, Be, Mg, Ba, V, Nb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Zn, Ga, Ru, Pd, Pt, Ag, B, Al, Sn, P, Sb, La or Ce.
In the above technical scheme, in the formula (I), R1Preferably optionally substituted C1-4Straight or branched chain alkyl, more preferably methyl.
In the above technical scheme, R2Preferably hydrogen, optionally substituted C1-5Straight 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, R3Preferably optionally substituted C1-10Straight or branched alkyl, optionally substituted C2-10Straight or branched alkenyl, optionally substituted C3-10A straight or branched chain cycloalkyl group. Preferably at least one of methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, pentanol, hexanol or cyclohexanol.
In the above technical scheme, the dosage of the alcohol compound is as follows: the mass fraction of the alcohol compound accounts for 0.01-99.99%, preferably 1-90%, and more preferably 10-60% of the total mass of the alcohol compound and the raw material with the structural formula (I).
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/Al2O35 to 100, preferably SiO2/Al2O3＝6～35。
In the above technical solution, the binder is selected from at least one of silica sol, pseudo-boehmite, alumina, kaolin, montmorillonite or bentonite, preferably at least one of pseudo-boehmite, alumina or silica sol.
In the technical scheme, the content of the molecular sieve in the molecular sieve composition is preferably 30-70 parts by weight, the content of the binder is preferably 30-70 parts by weight, and the content of the auxiliary agent is preferably 0.01-6 parts by weight.
In the above technical scheme, the auxiliary agent is preferably at least one selected from Ca, K, Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ga, Ru, Pd, Pt, Ag, B, Sn, P, La or Ce; more preferably at least one selected from Zn, Ga or Sn.
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.
The auxiliary agent may be introduced during the production of the molecular sieve composition or after the production of the molecular sieve composition, or may be introduced into the molecular sieve first, and then the molecular sieve composition may be produced by using the molecular sieve thus obtained, without any particular limitation. As a method for introducing the auxiliary, there may be mentioned, for example, those conventionally used in the art, particularly an ion exchange method or an impregnation method. In these processes, the auxiliaries are generally used in the form of precursors. For this reason, examples of the precursor of the metal assistant include a nitrate, a sulfate, an acetate, a chloride, and the like of the metal, examples of the precursor of the boron assistant include boric acid and borax, and examples of the precursor of the phosphorus assistant include diammonium hydrogen phosphate.
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 alcohol, and carbon deposition on the surface of the catalyst and in pore channels is removed in situ by introducing water generated in the hydroxyl removal process of an alcohol compound under the aromatization condition to react to form CO, so that the carbon deposition is removed, the aromatization activity of the catalyst is recovered, the service life of the catalyst is 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 1308 hours, and a good technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
Weighing 35 g of silicon-aluminium ratio of 25ZSM-5 and 35 g of gamma-alumina are mixed, 2.7 g of sesbania powder is added, and the mixture is mixed evenly. 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. Drying the obtained catalyst precursor at 120 deg.C for 8 hr, calcining at 500 deg.C for 2 hr, and soaking Zn (NO) with equal volume3)2And the Zn addition is 1 percent, and the molecular sieve catalyst is obtained by roasting after drying.
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 200 ℃ 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 24 g.
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 levulinic acid, 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 levulinic acid was 99%, and T60 was 96 hours.
[ example 1 ]
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. Drying the obtained catalyst precursor at 120 deg.C for 8 hr, calcining at 500 deg.C for 2 hr, and soaking Zn (NO) with equal volume3)2And the Zn addition is 1 percent, and the molecular sieve catalyst is obtained by roasting after drying.
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 200 ℃ 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 24 g.
Catalyst Activity evaluation on solidThe reaction is carried out on a fixed bed, the mass of a catalyst is 3 g, the reaction substrate is levulinic acid and methanol (60/40), 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 levulinic acid was 96%, and T60 was 1302 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 ℃, roasted for 2 hours at 500 ℃, and impregnated with Cu (NO) in equal volume3)2And the Cu addition amount is 2%, and the molecular sieve catalyst C2 is obtained by drying and roasting.
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 levulinic acid + ethanol (50/50), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And a temperature of 420 ℃. After the reaction was completed, the conversion of levulinic acid was 92% and T60 was 1219 hours.
[ example 3 ]
Weighing 30 g of wood, placing the wood in a pressure kettle, adding 300 g of ethanol, adding 5mol/L sulfuric acid solution with the water mass of 7%, heating to 200 ℃ for reaction for 30 minutes, 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 production amount of the levulinic acid is 10.5 g.
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 content of 5.5 percent of nitric acid, kneading and forming, and adding Ga (NO) in the kneading process3)2And the addition amount of Ga is 1 percent of the mass of the molecular sieve, 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.
Catalyst activityThe qualitative evaluation was carried out on a fixed bed under the reaction conditions of a catalyst mass of 3 g, levulinic acid + methanol as the reaction substrate (60/40), and a weight space velocity of 1.5 hours-1Hydrogen pressure 1.0MPa, flow 50ml min-1And a temperature of 420 ℃. After the reaction was complete, the levulinic acid conversion was 84%, and T60 was 1266 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking boric acid with the same volume, wherein the addition amount of B is 1%, and roasting after drying 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 levulinic acid + methanol (40/60), and the weight space velocity is 1.0 hour-1Hydrogen pressure 4.0MPa, flow 50ml min-1And the temperature is 470 ℃. After the reaction was complete, the levulinic acid conversion was 94% and T60 was 1136 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking ammonium molybdate by using the same volume, wherein the addition of Mo is 4%, and roasting after drying 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 methyl levulinate + ethanol (80/20), and the weight space velocity is 1.0 hour-1Hydrogen pressure 3.0MPa, flow 50ml min-1And the temperature is 380 ℃. After the reaction was complete, the conversion of methyl levulinate was 94% and T60 was 1081 h.
[ 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking lanthanum nitrate by using the same volume, wherein the addition amount of La is 1%, and roasting after drying 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 methyl levulinate + n-propanol (80/20), and the weight space velocity is 5.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1The temperature is 480 ℃. After the reaction was complete, the conversion of methyl levulinate was 86% and T60 was 1133 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking cerium nitrate by adopting the same volume, wherein the addition amount of Ce is 1%, and roasting after drying 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 ethyl levulinate + methanol (99/1), and the weight space velocity is 3.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 550 ℃. After the reaction was complete, the ethyl levulinate conversion was 91% and T60 was 1270 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking tin chloride in an equal volume, wherein the addition amount of Sn is 1%, and roasting after drying to obtain the molecular sieve catalyst C6.
Evaluation of catalyst Activity the catalyst was evaluated on a fixed bed and reactedThe weight of the catalyst is 3 g, the reaction substrate is ethyl levulinate + isopropanol (90/10), and the weight space velocity is 1.0 h-1Hydrogen pressure 5.0MPa, flow 20ml min-1And the temperature is 400 ℃. After the reaction was complete, the ethyl levulinate conversion was 95% and T60 was 1117 hours.
[ example 9 ]
60 g of ZSM-5 powder with a silica-alumina ratio of 50 is weighed and ion-exchanged for 2 hours at 90 ℃ with 180 ml of aqueous solution containing lanthanum nitrate and cerium nitrate. The mass of the metals La and Ce in the solution is 1 percent of that of the solid molecular sieve powder respectively. After the exchange is finished, drying is carried out, 35 g of ZSM-5 with the silica-alumina ratio of 50 is weighed and mixed with 35 g of gamma-alumina, 2.7 g of sesbania powder is added, and the mixture is uniformly mixed. 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 butyl levulinate + butanol (95/5) and the weight space velocity is 2.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was complete, the conversion of butyl levulinate was 81% and T60 was 1194 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 content of nitric acid of 5.5%, kneading and molding, adding copper nitrate and zinc nitrate in the kneading process, wherein the adding amount of copper and zinc is 1% and 1% of the solid mass of the molecular sieve, 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 was carried out on a fixed bed under reaction conditions of a catalyst mass of 3 g, a reaction substrate of butyl levulinate + isobutanol (95/5), and a weight space velocity of 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction is finished, levulinic acidThe butyl ester conversion was 97% and T60 was 1089 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 phosphoric acid aqueous solution with the phosphoric acid content of 5.5 percent by weight, kneading and molding, adding silver nitrate in the kneading process, wherein the adding amount of Ag is 1 percent of the solid mass of the molecular sieve, 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 methyl levulinate + amyl alcohol (95/5), and the weight space velocity is 3.0 hours-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 450 ℃. After the reaction was complete, the conversion of methyl levulinate was 93% and T60 was 1158 hours.
[ example 12 ]
60 g of Y molecular sieve with the silica-alumina ratio of 8 is weighed and subjected to ion exchange for 2 hours at 90 ℃ with 180 ml of aqueous solution containing nickel nitrate. The mass of the metal Ni in the solution is 5 percent of that of the solid molecular sieve powder respectively. And drying after the exchange is finished, weighing 70 g of Y molecular sieve with the silica-alumina ratio of 8, mixing with 30 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 C12.
The evaluation of the catalyst activity was carried out on a fixed bed under reaction conditions of a catalyst mass of 3 g, a reaction substrate of methyl levulinate + hexanol (95/5), a weight space velocity of 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was complete, the conversion of methyl levulinate was 95% and T60 was 1308 hours.
[ example 13 ]
180 g of Y molecular sieve with the silicon-aluminum ratio of 8 are weighed and subjected to ion exchange for 2 hours at 90 ℃ with 180 ml of aqueous solution containing gallium nitrate. The mass of metal Ga in the solution is respectively 2 percent of that of the solid molecular sieve powder. Drying after the exchange is finished, 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 was carried out on a fixed bed under reaction conditions of a catalyst mass of 3 g, a reaction substrate of methyl levulinate + cyclohexanol (95/5), and a weight space velocity of 1.0 hour-1Hydrogen pressure 4.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was complete, the conversion of methyl levulinate was 81% and T60 was 1062 hours.
[ example 14 ]
Weighing 50 g of beta 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 nitric acid of 5.5 percent, adding magnesium chloride in the kneading process, 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 methyl levulinate + methanol (85/15), and the weight space velocity is 1.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was complete, the conversion of methyl levulinate was 98% and T60 was 1201 hours.
[ example 15 ]
60 g of beta with the silica-alumina ratio of 50 and 40 g of pseudo-boehmite are weighed and mixed, and 3.9 g of sesbania powder is added and mixed evenly. 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking ammonium molybdate by using the same volume, wherein the addition amount of Mo is 6%, and roasting after drying to obtain the molecular sieve catalyst C15.
Evaluation of catalyst ActivityThe reaction is carried out on a fixed bed, the mass of a catalyst is 3 g, the reaction substrate is butyl levulinate + ethanol (80/20), and the weight space velocity is 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 460 ℃. After the reaction was complete, the conversion of butyl levulinate was 99% and T60 was 1220 hours.
[ example 16 ]
Weighing 70 g of beta with the silica-alumina 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 nitric acid aqueous solution with the mass percentage of 5.5 percent of nitric acid, kneading, molding and extruding strips. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking niobium nitrate with the same volume, wherein the addition amount of Nb is 1%, and roasting after drying 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 butyl levulinate + ethanol (95/5), 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 complete, the conversion of the butyl levulinate was 94% and T60 was 1189 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking ammonium tungstate by using the same volume, wherein the addition amount of W is 1%, and roasting after drying 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 butyl levulinate + methanol (95/5), and the weight space velocity is 1.0 h-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was complete, the conversion of butyl levulinate was 92% and T60 was 1278 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. Drying the obtained catalyst precursor at 120 ℃ for 8 hours, roasting at 500 ℃ for 2 hours, soaking manganese nitrate with the same volume, wherein the addition amount of Mn is 3%, and roasting after drying to obtain the molecular sieve catalyst C18.
Evaluation of catalyst Activity evaluation was carried out on a fixed bed under reaction conditions of 3 g of catalyst mass, 3 g of butyl levulinate + methanol as reaction substrate (95/5), weight space velocity of 1.0 hour-1Hydrogen pressure 1.0MPa, flow 50ml min-1And the temperature is 400 ℃. After the reaction was complete, the conversion of the butyl levulinate was 94% and T60 was 1082 hours.
TABLE 1
Claims (17)
1. An aromatization method comprising adding an alcohol compound R into an alcohol compound3A step of contacting a raw material with a catalyst in the presence of OH under aromatization reaction conditions to produce aromatic hydrocarbons; wherein the starting material has the structural formula (I):
in the formula (I), R1Is C1-8Straight or branched alkyl, C2-8Straight or branched alkenyl; r2Is hydrogen, C1-10A straight chain or branched chain alkyl group, wherein n is a positive integer of 1-6;
R3is C1-20Straight or branched alkyl, C2-20Straight-chain or branched alkenyl, C3-20A straight or branched chain cycloalkyl group;
the catalyst is a molecular sieve composition comprising the following components:
a) 20-80 parts by weight of a molecular sieve; the molecular sieve is selected from at least one of ZSM type molecular sieve, Y type molecular sieve, Beta type molecular sieve, L type molecular sieve or MCM type molecular sieve;
b) 20-80 parts by weight of a binder;
c) 0.01-10 parts by weight of an auxiliary agent; the auxiliary agent is at least one of Na, Ca, K, Be, Mg, Ba, V, Nb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Zn, Ga, Ru, Pd, Pt, Ag, B, Al, Sn, P, Sb, La or Ce;
wherein the dosage of the alcohol compound is as follows: the mass fraction of the alcohol compound accounts for 10-90% of the total mass of the alcohol compound and the raw material with the structural formula (I);
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 process according to claim 1 characterized in that in formula (I), R1Is C1-4A linear or branched alkyl group; r2Is hydrogen, C1-5The alkyl group is a straight chain or branched chain alkyl group, and n is a positive integer of 1-4.
3. The aromatization process according to claim 2 characterized in that in formula (I), R1Is methyl; r2Is hydrogen; n = 2.
4. The aromatization process according to claim 1 characterized in that R3Is C1-10Straight or branched alkyl, C2-10Straight-chain or branched alkenyl, C3-10A straight or branched chain cycloalkyl group.
5. The aromatization process according to claim 1 characterized in that the amount of the alcohol compound is: the mass fraction of the alcohol compound accounts for 10-60% of the total mass of the alcohol compound and the raw material with the structural formula (I).
6. The aromatization process 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 according to claim 1 characterized in that the ZSM-type molecular sieve has a silica to alumina molar ratio of SiO2/Al2O3= 10-500; Si/Al molar ratio SiO of Y-type molecular sieve2/Al2O3=2 to 70; silicon to aluminum molar ratio SiO of Beta type molecular sieve2/Al2O3= 10-150; silicon-aluminum molar ratio SiO of MCM type molecular sieve2/Al2O3=20 to 250; Si/Al molar ratio SiO of L-type molecular sieve2/Al2O3=5~100。
8. The aromatization process according to claim 7 characterized in that the ZSM-type molecular sieve has a silica to alumina molar ratio of SiO2/Al2O3=15 to 100; Si/Al molar ratio SiO of Y-type molecular sieve2/Al2O3= 3 to 50; silicon to aluminum molar ratio SiO of Beta type molecular sieve2/Al2O3=15 to 65; silicon-aluminum molar ratio SiO of MCM type molecular sieve2/Al2O3= 40 to 150; Si/Al molar ratio SiO of L-type molecular sieve2/Al2O3=6~35。
9. The aromatization process according to claim 1 characterized in that in the molecular sieve composition the molecular sieve is present in an amount of 30 to 70 parts by weight, the binder is present in an amount of 30 to 70 parts by weight and the promoter is present in an amount of 0.01 to 6 parts by weight.
10. The aromatization process according to claim 1 characterized in that the binder is selected from at least one of silica sol, pseudoboehmite, alumina, kaolin, montmorillonite or bentonite.
11. The aromatization process according to claim 1 characterized in that the promoter is selected from at least one of Ca, K, Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ga, Ru, Pd, Pt, Ag, B, Sn, P, La or Ce.
12. The aromatization process according to claim 11 characterized in that the promoter is selected from at least one of Zn, Ga or Sn.
13. The aromatization process according to claim 1 characterized in that the feedstock is derived from a biomass material.
14. The aromatization process 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.
15. The aromatization process according to claim 1 characterized in that the process further comprises the step of subjecting biomass material to catalytic conversion to obtain the feedstock.
16. 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 15; and
a step of separating p-xylene from the aromatic hydrocarbon.
17. A process for producing terephthalic acid, comprising the steps of:
a step of producing paraxylene according to the method of claim 16; and
a step of converting p-xylene into terephthalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610649375.XA CN107721794B (en) | 2016-08-10 | 2016-08-10 | Aromatization process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610649375.XA CN107721794B (en) | 2016-08-10 | 2016-08-10 | Aromatization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107721794A CN107721794A (en) | 2018-02-23 |
| CN107721794B true CN107721794B (en) | 2020-04-17 |
Family
ID=61199984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610649375.XA Active CN107721794B (en) | 2016-08-10 | 2016-08-10 | Aromatization process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107721794B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285151B (en) * | 2018-01-10 | 2020-02-14 | 中科合成油技术有限公司 | Ce isomorphous substituted LTL molecular sieve and preparation method thereof |
| CN114956946B (en) * | 2022-05-19 | 2023-08-15 | 中国科学院广州能源研究所 | Method for preparing monocyclic aromatic hydrocarbon by catalyzing rapid pyrolysis of cassava residues through modified molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058807A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing arene by utilizing methanol |
| CN104841473A (en) * | 2015-04-21 | 2015-08-19 | 东南大学 | Preparation method of alcohol aromatization catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5504493B2 (en) * | 2009-03-02 | 2014-05-28 | 国立大学法人 鹿児島大学 | Levulinic acid production apparatus, levulinic acid separation apparatus, and apparatus for producing hydrocarbons from levulinic acid |
-
2016
- 2016-08-10 CN CN201610649375.XA patent/CN107721794B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058807A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing arene by utilizing methanol |
| CN104841473A (en) * | 2015-04-21 | 2015-08-19 | 东南大学 | Preparation method of alcohol aromatization catalyst |
Non-Patent Citations (1)
| Title |
|---|
| In-situ catalytic upgrading of biomass pyrolysis vapor:Co-feeding with methanol in a multi-zone fixed bed reactor;Masoud Asadieraghi, et al.,;《Energy Conversion and Management》;20150116;第92卷;第448-458页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107721794A (en) | 2018-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102356149B1 (en) | Catalyst for pyrolysis of feedstock | |
| JP6877367B2 (en) | Method for producing aromatic hydrocarbons, p-xylene and terephthalic acid | |
| CN101684059A (en) | Method for producing propylene and ethylene through catalytic cracking of olefins | |
| CN107721794B (en) | Aromatization process | |
| CN101233213A (en) | Process for production of light olefins from hydrocarbon feedstock | |
| CN106316766B (en) | The method of aromatisation | |
| CN107586245B (en) | Aromatization process | |
| CN101590421A (en) | The catalyst of a kind of olefin catalytic cracking to produce propylene and ethene and application thereof | |
| CN106316763B (en) | The method of lactone compound aromatisation production aromatic hydrocarbons | |
| CN107721793B (en) | Process for producing aromatic hydrocarbons | |
| CN107721792B (en) | Process for producing aromatic hydrocarbon | |
| JP6976679B2 (en) | Methods for Producing Aromatic Hydrocarbons, P-Xylene and Terephthalic Acid | |
| CN113385215B (en) | Preparation method and application of catalyst for preparing propane by hydro-upgrading | |
| CN107586243B (en) | Process for producing aromatic hydrocarbon | |
| CN107586242B (en) | Aromatization process | |
| EP3312285B1 (en) | Method of preparing aromatic hydrocarbon, p-xylene and terephthalic acid, and apparatus producing aromatic hydrocarbon | |
| CN107721790B (en) | Process for producing aromatic hydrocarbon | |
| CN107586244B (en) | Process for producing aromatic hydrocarbon | |
| CN107721788B (en) | Method for producing aromatic hydrocarbon by aromatization | |
| CN107586246B (en) | Method for producing aromatic hydrocarbon by aromatization | |
| CN107721789B (en) | Method for aromatizing lactone compounds | |
| CN107721795B (en) | Process for producing aromatic hydrocarbon | |
| CN111116283A (en) | Method for producing aromatic hydrocarbon by using methanol and fusel oil as raw materials | |
| CN107540499B (en) | Method for maintaining high aromatic selectivity in process of preparing aromatic hydrocarbon from methanol | |
| CN107586240B (en) | Process for producing aromatic hydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |