CN111377785A - Method for producing aromatic hydrocarbon from methanol - Google Patents

Method for producing aromatic hydrocarbon from methanol Download PDF

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Publication number
CN111377785A
CN111377785A CN201811617515.0A CN201811617515A CN111377785A CN 111377785 A CN111377785 A CN 111377785A CN 201811617515 A CN201811617515 A CN 201811617515A CN 111377785 A CN111377785 A CN 111377785A
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reaction
methanol
product
catalyst
aromatic hydrocarbon
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冯丽梅
徐亚荣
蒋斌波
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention provides a method for producing aromatic hydrocarbon by methanol, which comprises the following steps: 1) carrying out a first reaction on methanol in the presence of a catalyst to produce a first product; then adding a diluent to carry out a second reaction to obtain a second product; 2) separating the second product to obtain the aromatic hydrocarbon; wherein the first product comprises dimethyl ether. The method firstly converts methanol into dimethyl ether, and then uses reactants including dimethyl ether to further prepare aromatic hydrocarbon, so that the heat in the whole reaction process is more controllable, and the problem that the aromatization reaction is difficult to normally carry out due to the generation of a large amount of heat in the direct aromatization reaction of methanol is avoided.

Description

Method for producing aromatic hydrocarbon from methanol
Technical Field
The invention relates to a method for producing aromatic hydrocarbon, in particular to a method for producing aromatic hydrocarbon from methanol, belonging to the technical field of coal chemical industry application.
Background
Aromatic hydrocarbon, as a basic raw material of petrochemical industry, plays an important role in the modern national economy of China. Among them, benzene, toluene and xylene, as three most basic light aromatic compounds (BTX), can be used for synthesizing a series of chemical products such as plastics, fibers, rubber, etc. Currently, about 97% of the aromatics worldwide are produced by the traditional petroleum route. In consideration of the characteristic energy structure of 'rich coal, lack of oil and little gas' in China, the development of a new technology for producing aromatic hydrocarbon by replacing petroleum resources with coal resources is of great importance.
Production of CO and H by coal gasification as raw material in coal chemical industry field2The technology for synthesizing the methanol is mature day by day, and in recent years, the methanol production capacity in China is seriously surplus. The development of the technology for directly preparing aromatic hydrocarbon (MTA) from coal-based methanol with rich resources can make up for the shortage of aromatic hydrocarbon demand in the market on one hand, and provide a way for surplus methanol on the other hand, improve the additional value of downstream products thereof, and has strategic significance.
As early as 1977, Mobil provided for the first time a method for converting methanol and oxygenates to hydrocarbons such as aromatics on ZSM-5.
The process of preparing aromatic hydrocarbon from methanol is generally regarded as the process of aromatization reaction of methanol. Experiments show that a large amount of heat is released when the methanol is subjected to direct aromatization, the heat is not beneficial to the aromatization reaction and simultaneously increases the coke content, so that the conversion rate of the methanol to the aromatic hydrocarbon is reduced, and the coke content can lead the catalyst to be inactivated so as to further reduce the possibility of the aromatization reaction.
Disclosure of Invention
The invention provides a method for producing aromatic hydrocarbon by methanol, which firstly converts the methanol into dimethyl ether, and then further prepares the aromatic hydrocarbon by reactants including the dimethyl ether, thereby ensuring that the heat in the whole reaction process is more controllable, and avoiding the problem that the aromatization reaction is difficult to normally carry out due to the generation of a large amount of heat in the direct aromatization reaction of the methanol.
The invention provides a method for producing aromatic hydrocarbon by methanol, which comprises the following steps:
1) carrying out a first reaction on methanol in the presence of a catalyst to produce a first product; then adding a diluent to obtain a second product;
2) separating the second product to obtain the aromatic hydrocarbon;
wherein the first product comprises dimethyl ether.
The method for producing the aromatic hydrocarbon by using the methanol, wherein the mass fraction of the dimethyl ether in the first product is 10-90%.
The method for producing the aromatic hydrocarbon by using the methanol comprises the steps of performing a first reaction at a reaction temperature of 200-300 ℃, at a reaction pressure of 0.1-3MPa and at a reaction space velocity of 0.1-10/h.
The method for producing aromatic hydrocarbons from methanol as described above, further comprising the step of subjecting the remaining components obtained by the separation treatment as a raw material to the first reaction with the methanol.
The method for producing aromatic hydrocarbons from methanol as described above, wherein the diluent is nitrogen and/or water vapor.
The method for producing the aromatic hydrocarbon by using the methanol, wherein in the second reaction, the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-3Mpa, and the reaction space velocity is 0.1-10/h.
The method for producing aromatic hydrocarbons from methanol as described above, wherein the mass ratio of the diluent to the raw material of the first reaction is (0.1-10): 1.
the method for producing aromatic hydrocarbons from methanol as described above, wherein the mass ratio of the remaining components to the methanol is (0.1 to 10): 1.
the method for producing aromatic hydrocarbons from methanol as described above, wherein the first reaction is performed in a first moving bed reactor, and the second reaction is performed in a second moving bed reactor.
The method for producing aromatic hydrocarbons from methanol as described above, wherein the catalyst is a modified ZSM-5 molecular sieve catalyst.
The method for producing the aromatic hydrocarbon by using the methanol, wherein the modified ZSM-5 molecular sieve catalyst comprises 0.5-20% of modified elements by mass.
The implementation of the invention at least comprises the following advantages:
1. the method for producing the aromatic hydrocarbon by the methanol comprises the steps of dividing the reaction into etherification reaction and aromatization reaction, converting the methanol into the methyl ether firstly, and then preparing the aromatic hydrocarbon by taking the methyl ether as a raw material for aromatization reaction, wherein the two-stage reaction releases balanced heat, so that the method is not only suitable for normal operation of the aromatization reaction, and is capable of improving the conversion rate of the methanol into the aromatic hydrocarbon, but also reducing the coke amount in the reaction process, and is beneficial to maintaining the activity of the catalyst and prolonging the service life of the catalyst;
2. the method for producing the aromatic hydrocarbon by using the methanol realizes the controllability of reaction heat, so that the preparation efficiency of the aromatic hydrocarbon can be maximized by increasing the reaction amount of the methanol;
3. the method for producing the aromatic hydrocarbon by using the methanol adopts the moving bed reactor, so that not only can the continuous regeneration of the catalyst be effectively realized, the activity maximization of the catalyst be ensured, but also the abrasion degree of the catalyst can be reduced, and the aromatic hydrocarbon can be efficiently and stably output;
4. the method for producing the aromatic hydrocarbon by using the methanol can effectively recycle the non-aromatic hydrocarbon components in the reaction product, and take the non-aromatic hydrocarbon components as the reaction raw material for reaction again, so that the heating consumption of the first reaction can be saved, the utilization rate of the raw material can be effectively improved, and the yield of the aromatic hydrocarbon can be further improved.
Drawings
FIG. 1 is a flow chart of a process for producing aromatic hydrocarbons from methanol according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
FIG. 1 is a flow chart of a method for producing aromatic hydrocarbons from methanol according to the present invention, please refer to FIG. 1.
The invention provides a method for producing aromatic hydrocarbon by methanol, which comprises the following steps:
s101: carrying out a first reaction on methanol in the presence of a catalyst to produce a first product; a diluent is then added to carry out a second reaction to obtain a second product.
Wherein the first product comprises dimethyl ether.
In the invention, the first reaction is etherification reaction, namely, the dimethyl ether is generated by taking methanol as a raw material under the action of a catalyst.
The etherification reaction avoids a large amount of heat which is necessarily released by the direct aromatization reaction of the methanol, thereby being beneficial to the normal operation of the aromatization reaction of the dimethyl ether, ensuring that the dimethyl ether can generate the aromatization reaction at normal temperature to generate aromatic hydrocarbon, effectively improving the conversion rate of the methanol to the aromatic hydrocarbon, and also avoiding the phenomenon of overhigh coke content of the catalyst caused by overhigh heat, thereby further prolonging the service life of the catalyst.
In addition, the heat is controlled by dividing the flow in stages, so that the preparation amount of the aromatic hydrocarbon can be further increased by increasing the quality of the methanol participating in the reaction, and the preparation efficiency of the reaction is effectively improved.
It can be understood that the first product generated by the first reaction includes not only dimethyl ether but also methanol which is not completely reacted and water generated by methanol cracking.
In order to be able to promote the first reaction and to convert more methanol to dimethyl ether, the reaction parameters of the first reaction may be controlled. Through the research of the inventor, when the mass fraction of the methanol in the first product is 1-10% and the mass fraction of the dimethyl ether is 10-90%, the yield of the aromatic hydrocarbon can be effectively improved on the premise of ensuring controllable heat.
Specifically, the content of the methanol and the dimethyl ether can be realized by controlling the reaction temperature of the first reaction to be 200-300 ℃, the reaction pressure to be 0.1-3Mpa and the reaction space velocity to be 0.1-10/h.
Further, the catalyst of the invention is a modified ZSM-5 molecular sieve catalyst. Wherein, the modifying element can be metal and/or nonmetal.
Specifically, if the modifying element is a metal element, the modifying element is selected from one or more of Ga, Zn, Sn, Ni, Mn, Mg, Cr, Cu, Ag, Pd, Ir and Ru;
if the modifying element is a non-metallic element, the modifying element is selected from P and/or B.
The modification method can load a salt solution of a modification element on the ZSM-5 molecular sieve, and then convert the salt solution into an oxide of the modification element to load on the ZSM-5 molecular sieve in a drying and roasting mode, thereby completing the modification of the ZSM-5 molecular sieve.
Wherein, in order to enhance the catalytic activity of the catalyst, the modifying element accounts for 0.5 to 20 percent of the mass of the catalyst.
In order to ensure the catalytic effect of the catalyst, the carbon content of the catalyst is less than 0.5 wt%.
And when the mass fraction of the dimethyl ether in the first product is 10-90%, mixing the first product with a diluent, and carrying out a second reaction under the continuous catalysis of the catalyst to obtain a second product.
Wherein the diluent is nitrogen and/or water vapor.
The diluent is mainly used for controlling the second reaction, i.e., the effect of temperature rise of the aromatization reaction, and does not participate in the aromatization reaction itself but merely serves to reduce the partial pressure of the feedstock and acts as a heat carrier. Specifically, the mass ratio of the diluent to the raw material (methanol) in the first reaction is (0.1-10): 1.
after the first product is mixed with the diluent, in the process of producing the second product in the presence of the catalyst, the aromatization reaction of dimethyl ether and the aromatization reaction of methanol are included, but because the first product is mainly dimethyl ether, the heat released when the methanol is converted into the low-carbon hydrocarbon in the second reaction in the invention can not seriously affect the generation of aromatic hydrocarbon, and the heat can be used as a heat source of the second reaction to ensure that the second reaction is normally carried out, thereby effectively saving energy consumption.
Wherein the reaction temperature of the second reaction is 450-550 ℃, the reaction pressure is 0.1-3Mpa, and the reaction space velocity is 0.1-10/h.
In addition, when the catalyst completes the catalysis of the first reaction, the catalyst, which is a catalyst having a carbon content of more than 0.5 wt%, can continue to catalyze the second reaction. Generally, after the first reaction, the carbon content of the catalyst is 3-10%.
The catalyst can be continuously used and respectively catalyzes two different types of reactions, so that the utilization rate of the catalyst is obviously improved. In addition, the carbon content of the catalyst in the general reaction for directly preparing the aromatic hydrocarbon by the methanol is not higher than 1%, but the invention can still obtain the aromatic hydrocarbon when the carbon content of the catalyst is 3-10% by carrying out the methanol aromatization reaction in a segmented way, thereby reducing the dependence requirement of the aromatic hydrocarbon yield on the activity of the catalyst and further improving the yield of the aromatic hydrocarbon.
In the process of the second reaction, if the carbon content of the catalyst is significantly higher than 10%, the catalyst needs to be regenerated. That is, the catalyst is removed from the second reaction zone where the second reaction is performed to the regenerator, and is regenerated in the regenerator and then re-enters the first reactor where the first reaction is performed to participate in the first reaction.
S102: and separating the second product to obtain the aromatic hydrocarbon.
In the second product, aromatic hydrocarbons (toluene, benzene and xylene), unreacted dimethyl ether, unreacted methanol, water produced by methanol cracking, C1-C5 lower hydrocarbons and hydrocarbons above C6 are mainly included, so that the aromatic hydrocarbons can be separated from the second product by adopting separation treatment.
In particular, the separation treatment is an aromatic extraction separation common in the art, such as a rectification separation.
Further, after the separation treatment in S012 is completed, the remaining components in the second product, that is, the non-aromatic hydrocarbon portion (unreacted dimethyl ether, unreacted methanol, C1 to C5 lower hydrocarbons and hydrocarbons of C6 or more) may be collected and input to the first reactor as the raw material for the first reaction to perform the first reaction, so that not only the utilization rate of the raw material can be improved, but also the yield of aromatic hydrocarbons can be further increased. Moreover, the heat carried by the non-aromatic hydrocarbon part can also be used as the heat required by the first reaction, thereby further reducing the dependence of the first reaction on an external heating device and reducing the energy consumption.
In the invention, the mass ratio of the rest components to the raw material methanol in the first reaction is (0.1-10): 1.
in the above case, the raw material for the first reaction includes not only methanol first introduced into the first reaction zone but also unreacted dimethyl ether, unreacted methanol, lower hydrocarbons of C1 to C5 and hydrocarbons of C6 or more from the second product, and therefore the amount of the diluent used should be based on the total amount of methanol first introduced into the first reaction zone, unreacted dimethyl ether in the second product, unreacted methanol, lower hydrocarbons of C1 to C5 and hydrocarbons of C6 or more.
In addition, the amount of non-aromatic fraction in the second product entering the first reaction zone can be adjusted, and the typical actual non-aromatic fraction in the second product input to the first reaction zone can be 50-100% of the total amount of non-aromatic fraction in the second product, with increased aromatics production achieved by adjusting the amount of non-aromatic fraction in the second product input to the first reaction zone.
In order to improve the catalytic activity of the catalyst and improve the utilization rate of the catalyst, the invention can adopt a moving bed to carry out reaction. Specifically, the moving length can realize continuous regeneration of the catalyst, ensure that the catalyst maintains higher activity to ensure efficient and stable output of the aromatic hydrocarbon, facilitate the conversion of the catalyst at the first reaction zone and the second reaction zone, and enable the catalyst to enter the second reaction zone as the catalyst to continuously catalyze the second reaction after the catalyst completes the first reaction.
Specifically, the first reaction may be carried out in a first moving bed reactor, and the second reaction may be carried out in a second moving bed reactor.
The first moving bed reactor can be formed by connecting a plurality of moving bed reactors in series, and the second moving bed reactor can be formed by connecting a plurality of moving bed reactors in series.
The method of the present invention will be described by taking, as an example, a moving bed reactor for the first reaction and a moving bed reactor for the second reaction.
Taking methanol as a raw material for a first reaction in a moving bed reactor in a first reaction zone, conveying a catalyst with carbon content less than 0.5% into the moving bed reactor in the first reaction zone, controlling the reaction temperature and the reaction pressure to reach a target temperature and a target pressure, contacting the methanol with the catalyst to perform a first reaction, and obtaining a first product after a period of time; wherein the first product comprises dimethyl ether with the mass fraction of the dimethyl ether being 10-90%, water produced by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
The carbon content of the catalyst after the reaction in the first reaction zone is 3-10%. The catalyst can be slowly moved downward by gravity, removed from the moving bed reactor of the first reaction zone and passed into the moving bed reactor of the second reaction zone.
Meanwhile, a first product at the outlet of the first reaction zone and a diluent are mixed and then enter a moving bed reactor of a second reaction zone, after the reaction temperature and the reaction pressure reach a target temperature and a target pressure, the first product is contacted with a catalyst to carry out a second reaction, and after a period of time, a second product is obtained; wherein the second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol
And separating the second product stream at the outlet of the second reaction zone to obtain target products of benzene, toluene and xylene, and all or part of the rest incompletely converted methanol and dimethyl ether and byproducts of C1-C5 hydrocarbons and C6+ hydrocarbons serving as return hydrocarbons to enter the first reaction zone for reaction again.
And after the catalyst finishes the second reaction in the second reaction zone, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
Hereinafter, the method for producing aromatic hydrocarbons from methanol according to the present invention will be described in detail with reference to the following examples.
Example 1
The method for producing the aromatic hydrocarbon by using the methanol comprises the following steps:
1) formation of the first product
Starting materials for the first reaction: methanol
Catalyst (carbon content less than 0.5%): the ZSM-5 molecular sieve modified by the zinc element is utilized, and the mass fraction of the zinc element in the ZSM-5 molecular sieve is 1 percent
A first reactor: moving bed reactor
Specifically, methanol and a catalyst are mixed in a moving bed reactor and then subjected to a first reaction to generate a first product.
The temperature of the first reaction is 250 ℃, the pressure is 0.5Mpa, and the space velocity of the methanol is 1/h.
Wherein the first product comprises dimethyl ether, water generated by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
In the first product, the mass fraction of dimethyl ether is 80%.
In the first product, the mass fraction of methanol was 20%.
2) Formation of the second product
After the catalyst completes the first reaction, the carbon content is 5%.
The catalyst slowly moves down by gravity, is removed from the moving bed reactor of the first reaction zone and enters the moving bed reactor of the second reaction zone.
And simultaneously, mixing the first product with a diluent, then feeding the mixture into a moving bed reactor in a second reaction zone, controlling the temperature of the second reaction to be 450 ℃, controlling the pressure to be 0.3Mpa and controlling the space velocity of the first product to be 1/h, and generating the second product.
The second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol.
Wherein, the diluent of the second reaction is nitrogen, and the mass ratio of the nitrogen to the raw materials in the first reaction is 3: 1.
3) separation of the second product
And (4) carrying out aromatic extraction separation on the second product, and collecting benzene, toluene and xylene.
In addition, the remaining components of the second product, i.e., C1-C5 hydrocarbons, C6+ other hydrocarbons, as well as unreacted dimethyl ether and methanol, are taken part in the first reaction as return hydrocarbons. Wherein the mass ratio of the return hydrocarbon to the methanol feedstock in the first reaction is 3: 7.
and after the second reaction of the catalyst in the second reaction zone is finished, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
After the catalyst was operated stably under the conditions of this example, the collected product was subjected to calculation and examination, and the results are shown in table 1.
Example 2
The method for producing the aromatic hydrocarbon by using the methanol comprises the following steps:
1) formation of the first product
Starting materials for the first reaction: methanol
Catalyst (carbon content less than 0.5%): the ZSM-5 molecular sieve modified by zinc element and gallium element, wherein the mass fraction of the zinc element in the ZSM-5 molecular sieve is 2 percent, and the mass fraction of the gallium element in the ZSM-5 molecular sieve is 1 percent
A first reactor: moving bed reactor
Specifically, methanol and a catalyst are mixed in a moving bed reactor and then subjected to a first reaction to generate a first product.
The temperature of the first reaction is 220 ℃, the pressure is 0.5Mpa, and the space velocity of the methanol is 2/h.
Wherein the first product comprises dimethyl ether, water generated by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
In the first product, the mass fraction of dimethyl ether was 70%.
In the first product, the mass fraction of methanol was 8%.
2) Formation of the second product
After the catalyst completes the first reaction, the carbon content is 3%.
The catalyst slowly moves down by gravity, is removed from the moving bed reactor of the first reaction zone and enters the moving bed reactor of the second reaction zone.
And simultaneously, mixing the first product with a diluent, then feeding the mixture into a moving bed reactor in a second reaction zone, controlling the temperature of the second reaction to be 470 ℃, controlling the pressure to be 0.4Mpa and controlling the space velocity of the first product to be 2/h, and generating the second product.
The second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol.
Wherein, the diluent of the second reaction is nitrogen, and the mass ratio of the nitrogen to the raw materials in the first reaction is 2: 1.
3) separation of the second product
And (4) carrying out aromatic extraction separation on the second product, and collecting benzene, toluene and xylene.
In addition, the remaining components of the second product, i.e., C1-C5 hydrocarbons, C6+ other hydrocarbons, as well as unreacted dimethyl ether and methanol, are taken part in the first reaction as return hydrocarbons. Wherein the mass ratio of the return hydrocarbon to the methanol feedstock in the first reaction is 4: 6.
and after the second reaction of the catalyst in the second reaction zone is finished, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
After the catalyst was operated stably under the conditions of this example, the collected product was subjected to calculation and examination, and the results are shown in table 1.
Example 3
The method for producing the aromatic hydrocarbon by using the methanol comprises the following steps:
1) formation of the first product
Starting materials for the first reaction: methanol
Catalyst (carbon content less than 0.5%): the ZSM-5 molecular sieve modified by silver element and boron element is characterized in that the mass fraction of the silver element in the ZSM-5 molecular sieve is 1 percent, and the mass fraction of the boron element in the ZSM-5 molecular sieve is 5 percent
A first reactor: moving bed reactor
Specifically, methanol and a catalyst are mixed in a moving bed reactor and then subjected to a first reaction to generate a first product.
The temperature of the first reaction is 270 ℃, the pressure is 2Mpa, and the space velocity of the methanol is 4/h.
Wherein the first product comprises dimethyl ether, water generated by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
In the first product, the mass fraction of dimethyl ether is 80%.
In the first product, the mass fraction of methanol was 2%.
2) Formation of the second product
After the catalyst completes the first reaction, the carbon content is 7%.
The catalyst slowly moves down by gravity, is removed from the moving bed reactor of the first reaction zone and enters the moving bed reactor of the second reaction zone.
Meanwhile, the first product and the diluent are mixed and then enter a moving bed reactor in a second reaction zone, the temperature of the second reaction is controlled to be 500 ℃, the pressure is controlled to be 0.5Mpa, and the space velocity of the first product is controlled to be 1.5/h, so that the second product is generated.
The second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol.
Wherein, the diluent of the second reaction is water vapor, and the mass ratio of the water to the raw materials in the first reaction is 5: 1.
3) separation of the second product
And (4) carrying out aromatic extraction separation on the second product, and collecting benzene, toluene and xylene.
In addition, the remaining components of the second product, i.e., C1-C5 hydrocarbons, C6+ other hydrocarbons, as well as unreacted dimethyl ether and methanol, are taken part in the first reaction as return hydrocarbons. Wherein the mass ratio of the return hydrocarbon to the methanol feedstock in the first reaction is 1: 9.
and after the second reaction of the catalyst in the second reaction zone is finished, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
After the catalyst was operated stably under the conditions of this example, the collected product was subjected to calculation and examination, and the results are shown in table 1.
Example 4
The method for producing the aromatic hydrocarbon by using the methanol comprises the following steps:
1) formation of the first product
Starting materials for the first reaction: methanol
Catalyst (carbon content less than 0.5%): the ZSM-5 molecular sieve modified by the zinc element is utilized, and the mass fraction of the zinc element in the ZSM-5 molecular sieve is 1 percent
A first reactor: moving bed reactor
Specifically, methanol and a catalyst are mixed in a moving bed reactor and then subjected to a first reaction to generate a first product.
The temperature of the first reaction is 250 ℃, the pressure is 1Mpa, and the space velocity of the methanol is 1/h.
Wherein the first product comprises dimethyl ether, water generated by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
In the first product, the mass fraction of dimethyl ether is 80%.
In the first product, the mass fraction of methanol was 3%.
2) Formation of the second product
After the catalyst completes the first reaction, the carbon content is 3%.
The catalyst slowly moves down by gravity, is removed from the moving bed reactor of the first reaction zone and enters the moving bed reactor of the second reaction zone.
Meanwhile, the first product and the diluent are mixed and then enter a moving bed reactor in a second reaction zone, the temperature of the second reaction is controlled to be 450 ℃, the pressure is controlled to be 0.3Mpa, and the space velocity of the first product is controlled to be 2.5/h, so that the second product is generated.
The second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol.
Wherein, the diluent of the second reaction is nitrogen, and the mass ratio of the nitrogen to the raw materials in the first reaction is 2: 1.
3) separation of the second product
And (4) carrying out aromatic extraction separation on the second product, and collecting benzene, toluene and xylene.
In addition, the remaining components of the second product, i.e., C1-C5 hydrocarbons, C6+ other hydrocarbons, as well as unreacted dimethyl ether and methanol, are taken part in the first reaction as return hydrocarbons. Wherein the mass ratio of the return hydrocarbon to the methanol feedstock in the first reaction is 2: 8.
and after the second reaction of the catalyst in the second reaction zone is finished, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
After the catalyst was operated stably under the conditions of this example, the collected product was subjected to calculation and examination, and the results are shown in table 1.
Example 5
The method for producing the aromatic hydrocarbon by using the methanol comprises the following steps:
1) formation of the first product
Starting materials for the first reaction: methanol
Catalyst (carbon content less than 0.5%): the ZSM-5 molecular sieve modified by zinc element and gallium element, wherein the mass fraction of the zinc element in the ZSM-5 molecular sieve is 2 percent, and the mass fraction of the gallium element in the ZSM-5 molecular sieve is 1 percent
A first reactor: moving bed reactor
Specifically, methanol and a catalyst are mixed in a moving bed reactor and then subjected to a first reaction to generate a first product.
The temperature of the first reaction is 220 ℃, the pressure is 0.5Mpa, and the space velocity of the methanol is 2/h.
Wherein the first product comprises dimethyl ether, water generated by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
In the first product, the mass fraction of dimethyl ether was 70%.
In the first product, the mass fraction of methanol was 10%.
2) Formation of the second product
After the catalyst completes the first reaction, the carbon content is 3%.
The catalyst slowly moves down by gravity, is removed from the moving bed reactor of the first reaction zone and enters the moving bed reactor of the second reaction zone.
And simultaneously, mixing the first product with a diluent, feeding the mixture into a moving bed reactor in a second reaction zone, controlling the temperature of the second reaction to be 470 ℃, controlling the pressure to be 0.4Mpa and controlling the space velocity of the first product to be 1.8/h, and generating the second product.
The second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol.
Wherein, the diluent of the second reaction is nitrogen, and the mass ratio of the nitrogen to the raw materials in the first reaction is 2: 1.
3) separation of the second product
And (4) carrying out aromatic extraction separation on the second product, and collecting benzene, toluene and xylene.
In addition, the remaining components of the second product, i.e., C1-C5 hydrocarbons, C6+ other hydrocarbons, as well as unreacted dimethyl ether and methanol, are taken part in the first reaction as return hydrocarbons. Wherein the mass ratio of the return hydrocarbon to the methanol feedstock in the first reaction is 2: 8.
and after the second reaction of the catalyst in the second reaction zone is finished, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
After the catalyst was operated stably under the conditions of this example, the collected product was subjected to calculation and examination, and the results are shown in table 1.
Example 6
The method for producing the aromatic hydrocarbon by using the methanol comprises the following steps:
1) formation of the first product
Starting materials for the first reaction: methanol
Catalyst (carbon content less than 0.5%): the ZSM-5 molecular sieve modified by silver element and boron element is characterized in that the mass fraction of the silver element in the ZSM-5 molecular sieve is 1 percent, and the mass fraction of the boron element in the ZSM-5 molecular sieve is 5 percent
A first reactor: moving bed reactor
Specifically, methanol and a catalyst are mixed in a moving bed reactor and then subjected to a first reaction to generate a first product.
The temperature of the first reaction is 270 ℃, the pressure is 2Mpa, and the space velocity of the methanol is 4/h.
Wherein the first product comprises dimethyl ether, water generated by methanol cracking, C1-C5 hydrocarbons, C6+ other hydrocarbons and methanol which is not completely reacted.
In the first product, the mass fraction of dimethyl ether was 70%.
In the first product, the mass fraction of methanol was 5%.
2) Formation of the second product
After the catalyst completes the first reaction, the carbon content is 7%.
The catalyst slowly moves down by gravity, is removed from the moving bed reactor of the first reaction zone and enters the moving bed reactor of the second reaction zone.
And simultaneously, mixing the first product with a diluent, feeding the mixture into a moving bed reactor in a second reaction zone, controlling the temperature of the second reaction to be 500 ℃, controlling the pressure to be 0.5Mpa and controlling the space velocity of the first product to be 1.2/h, and generating the second product.
The second product comprises benzene, toluene, xylene, C1-C5 hydrocarbons, C6+ other hydrocarbons, water, and unreacted dimethyl ether and methanol.
Wherein, the diluent of the second reaction is water vapor, and the mass ratio of the water to the raw materials in the first reaction is 5: 1.
3) separation of the second product
And (4) carrying out aromatic extraction separation on the second product, and collecting benzene, toluene and xylene.
In addition, the remaining components of the second product, i.e., C1-C5 hydrocarbons, C6+ other hydrocarbons, as well as unreacted dimethyl ether and methanol, are taken part in the first reaction as return hydrocarbons. Wherein the mass ratio of the return hydrocarbon to the methanol feedstock in the first reaction is 2.5: 7.5.
and after the second reaction of the catalyst in the second reaction zone is finished, the catalyst is removed from the moving bed reactor in the second reaction zone and is conveyed to a regeneration system for regeneration, and the regenerated catalyst with the carbon content less than 0.5 percent returns to the first reaction zone for circulation.
After the catalyst was operated stably under the conditions of this example, the collected product was subjected to calculation and examination, and the results are shown in table 1.
TABLE 1
Figure BDA0001926107750000141
Figure BDA0001926107750000151
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (11)

1. A method for producing aromatic hydrocarbon by methanol is characterized by comprising the following steps:
1) carrying out a first reaction on methanol in the presence of a catalyst to produce a first product; then adding a diluent to carry out a second reaction to obtain a second product;
2) separating the second product to obtain the aromatic hydrocarbon;
wherein the first product comprises dimethyl ether.
2. The method for producing the aromatic hydrocarbon by using the methanol as claimed in claim 1, wherein the mass fraction of the dimethyl ether in the first product is 10-90%.
3. The method for producing aromatic hydrocarbons from methanol according to claim 2, wherein the reaction temperature in the first reaction is 200-.
4. The method for producing aromatic hydrocarbons from methanol according to claim 3, further comprising the step of subjecting the remaining components obtained by the separation treatment as a raw material to the first reaction with the methanol.
5. The method for producing aromatic hydrocarbons from methanol according to claim 4, wherein the diluent is nitrogen and/or water vapor.
6. The method for producing aromatic hydrocarbons from methanol according to claim 5, wherein in the second reaction, the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-3MPa, and the reaction space velocity is 0.1-10/h.
7. The method for producing aromatic hydrocarbons from methanol according to claim 6, wherein the mass ratio of the diluent to the raw material of the first reaction is (0.1-10): 1.
8. the method for producing aromatic hydrocarbons from methanol according to claim 4, wherein the mass ratio of the remaining components to the methanol is (0.1-10): 1.
9. the method for producing the aromatic hydrocarbon by using the methanol as claimed in any one of claims 1 to 8, wherein the first reaction is carried out in a first moving bed reactor, and the second reaction is carried out in a second moving bed reactor.
10. The method for producing aromatic hydrocarbons from methanol according to claim 8, wherein the catalyst is a modified ZSM-5 molecular sieve catalyst.
11. The method for producing aromatic hydrocarbons from methanol according to claim 10, wherein the modified ZSM-5 molecular sieve catalyst contains 0.5-20% of modifying elements by mass.
CN201811617515.0A 2018-12-28 2018-12-28 Method for producing aromatic hydrocarbon from methanol Pending CN111377785A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103664482A (en) * 2013-12-03 2014-03-26 浙江大学 Reaction technology for converting oxygen-containing compound into aromatic hydrocarbons by using moving bed process
CN105111035A (en) * 2015-09-22 2015-12-02 西南化工研究设计院有限公司 Technology for co-producing arene through MTO (methanol to olefin)
CN106608786A (en) * 2015-10-22 2017-05-03 中国石油化工股份有限公司 Method for cooperatively producing ethylbenzene by preparing xylene from alcohol ether

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103664482A (en) * 2013-12-03 2014-03-26 浙江大学 Reaction technology for converting oxygen-containing compound into aromatic hydrocarbons by using moving bed process
CN105111035A (en) * 2015-09-22 2015-12-02 西南化工研究设计院有限公司 Technology for co-producing arene through MTO (methanol to olefin)
CN106608786A (en) * 2015-10-22 2017-05-03 中国石油化工股份有限公司 Method for cooperatively producing ethylbenzene by preparing xylene from alcohol ether

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