CN112920006A - Method for preparing aromatic hydrocarbon compound from ethanol - Google Patents
Method for preparing aromatic hydrocarbon compound from ethanol Download PDFInfo
- Publication number
- CN112920006A CN112920006A CN201911232567.0A CN201911232567A CN112920006A CN 112920006 A CN112920006 A CN 112920006A CN 201911232567 A CN201911232567 A CN 201911232567A CN 112920006 A CN112920006 A CN 112920006A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ethanol
- reaction
- acidic molecular
- catalyst
- 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.)
- Pending
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
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing aromatic compounds from ethanol, which comprises the steps of carrying out contact reaction on a raw material containing ethanol and carbon monoxide and an acidic molecular sieve catalyst in a reaction zone to obtain aromatic compounds; wherein the acidic molecular sieve catalyst does not contain a metal element. The method improves and stabilizes the selectivity of aromatic hydrocarbon, and prolongs the one-way service life of the catalyst. The performance of the catalyst subjected to ethanol aromatization inactivation in the carbon monoxide atmosphere is not obviously reduced after multiple regenerations.
Description
Technical Field
The application relates to a method for preparing an aromatic hydrocarbon compound by using ethanol, belonging to the field of chemical catalysis.
Background
Aromatic hydrocarbons, especially Benzene (Benzene), Toluene (Toluene) and Xylene (Xylene), collectively known as BTX, are second to ethylene and propylene in yield and scale, and their derivatives are widely used in chemical and fine chemicals such as fuels, petrochemicals, chemical fibers, plastics and rubbers.
Currently, aromatics are produced mainly from petroleum as feedstock, with 70% of BTX aromatics worldwide coming from catalytic reforming process units in oil refineries. The catalytic reforming technology uses naphtha as raw material, adopts the process types of semi-regeneration and continuous regeneration reforming, and generally adopts platinum-containing catalyst for catalytic reforming. Typical processes for catalytic reforming are represented by the CCR platformer process from UOP and the Aromizer process from IFP. In addition, the aromatic hydrocarbon production process in the petroleum route also comprises a gasoline hydrogenation technology, an aromatic hydrocarbon extraction technology, a heavy aromatic hydrocarbon light conversion technology and a light hydrocarbon aromatization technology.
With the continuous development of society, the demand of aromatic hydrocarbons in the world is continuously increased, however, the price of the aromatic hydrocarbons, particularly BTX, is kept high due to the increasing shortage of petroleum resources. In view of the current situation of energy structure of 'rich coal and lean oil' in China, the great development of coal chemical industry routes for preparing aromatic hydrocarbon has very important significance.
In the traditional reaction for preparing the aromatic hydrocarbon from the ethanol, a large amount of alkane is generated and the selectivity of the aromatic hydrocarbon is inhibited because the aromatic hydrocarbon is generated from the alkene and is accompanied with the hydrogen transfer reaction, so that the alkane is dehydrogenated by adopting an acidic ZSM-5 molecular sieve catalyst modified by metal additives such as zinc, gallium, silver and the like, and the selectivity of the aromatic hydrocarbon is improved. However, the metal is easy to sublimate or aggregate under the high temperature condition, the selectivity of the aromatic hydrocarbon is reduced quickly, the service life of the catalyst is short, the selectivity of BTX is not high, the performance of the catalyst is obviously reduced after regeneration, and the like, so that the industrial application of the catalyst is restricted.
Disclosure of Invention
According to one aspect of the application, a method for preparing aromatic hydrocarbon compounds from ethanol is provided, wherein raw materials containing ethanol and carbon monoxide pass through a reaction zone of a catalyst loaded with an acidic molecular sieve without metal elements to react under certain reaction conditions to prepare aromatic hydrocarbon. Carbon monoxide is added in the ethanol aromatization reaction, so that the selectivity of aromatic hydrocarbon can be improved and stabilized, and the one-way service life of the catalyst is prolonged. The performance of the catalyst subjected to ethanol aromatization inactivation in the carbon monoxide atmosphere is not obviously reduced after multiple regenerations.
The method for preparing the aromatic hydrocarbon compound by using the ethanol is characterized in that a raw material containing the ethanol and the carbon monoxide is in contact reaction with an acidic molecular sieve catalyst in a reaction zone to obtain the aromatic hydrocarbon compound;
wherein the acidic molecular sieve catalyst does not contain a metal element.
Optionally, the molar ratio of the carbon monoxide to the ethanol is greater than or equal to 1: 1.
Optionally, the molar ratio of the carbon monoxide to the ethanol is 20:1 to 100: 1.
Optionally, the molar ratio of the carbon monoxide to the ethanol is 20:1 to 40: 1.
Optionally, the acidic molecular sieve catalyst is selected from at least one of an RHO configuration acidic molecular sieve, a CHA configuration acidic molecular sieve, a FER configuration acidic molecular sieve, an MFI configuration acidic molecular sieve, an MOR configuration acidic molecular sieve, a FAU configuration acidic molecular sieve, and an EMT configuration acidic molecular sieve.
Optionally, the acidic molecular sieve catalyst is selected from at least one of a hydrogen form ZSM-5 molecular sieve, a hydrogen form ZSM-35 molecular sieve, a hydrogen form MOR molecular sieve.
Optionally, the acidic molecular sieve catalyst is a molecular sieve that has not been modified by metal promoter impregnation, ion exchange, physical mixing, and the like.
Optionally, the acidic molecular sieve catalyst is a hydrogen form of ZSM-5 molecular sieve without metal promoter impregnation, ion exchange and physical mixing.
Optionally, the hydrogen type ZSM-5 molecular sieve has one or more of a micro structure, a nano structure, a micro-pore structure and a meso-micro-pore structure.
Optionally, the acidic molecular sieve catalyst has an atomic ratio of silicon to aluminum of 3 to 200 Si/Al.
Optionally, the acidic molecular sieve catalyst has an atomic ratio of silicon to aluminum of 4 to 200 Si/Al.
Optionally, the atomic ratio of silicon to aluminum in the acidic molecular sieve catalyst is 10-40.
Optionally, the atomic ratio of silicon to aluminum in the acidic molecular sieve catalyst is 19-30 Si/Al.
Optionally, the reaction conditions of the reaction are:
the reaction temperature is 350-550 ℃, and the reaction pressure is 0.5-10 MPa.
Optionally, the reaction conditions of the reaction are:
the reaction temperature is 390-480 ℃, and the reaction pressure is 3-7 MPa.
Alternatively, the upper limit of the reaction temperature is selected from 550 ℃, 500 ℃, 480 ℃, 450 ℃ or 400 ℃, and the lower limit of the reaction temperature is selected from 350 ℃, 390 ℃, 400 ℃ or 450 ℃.
Alternatively, the upper limit of the reaction pressure is selected from 10MPa, 7MPa, 5MPa or 3MPa, and the lower limit of the reaction pressure is selected from 0.5MPa, 1MPa, 2MPa or 3 MPa.
Optionally, the reaction time is 5-100 h.
Preferably, the reaction time is 5 h.
Optionally, the mass space velocity of the ethanol is 0.01-20 h-1。
Preferably, the mass space velocity of the ethanol is 0.3-3 h-1。
Optionally, the upper limit of the mass space velocity of the ethanol is selected from 20h-1、15h-1、10h-1、5h-1Or 3h-1The lower limit of the mass space velocity of the ethanol is selected from 0.01h-1、0.3h-1、1h-1、2h-1Or 3h-1。
Optionally, the service life of the acidic molecular sieve catalyst after the regeneration treatment is more than or equal to 1000 h.
Optionally, the service life of the acidic molecular sieve catalyst after the regeneration treatment is more than or equal to 1100 h.
Optionally, the service life of the acidic molecular sieve catalyst after the regeneration treatment is more than or equal to 1200 h.
Optionally, the method for regenerating the acidic molecular sieve catalyst comprises: the deactivated catalyst is treated at high temperature in the presence of a mixed gas containing oxygen and nitrogen.
Optionally, the service life of the acidic molecular sieve catalyst after the regeneration treatment under the mixed gas containing oxygen and nitrogen is more than or equal to 1000 h.
Optionally, the reaction zone comprises one reactor or a plurality of reactors connected in series and/or parallel.
Optionally, the reactor is a fixed bed reactor, a moving bed reactor or a fluidized bed reactor that enables continuous reactions.
Preferably, the reactor is a fixed bed reactor.
The reactor is one or more fixed bed reactors. In the form of a continuous reaction. One or more fixed bed reactors may be used. When a plurality of fixed bed reactors are adopted, the reactors can be connected in series, in parallel or in a combination of series and parallel.
According to the method for preparing the aromatic hydrocarbon compound by using the ethanol, the conversion rate of the ethanol reaches 100 percent.
According to the method for preparing the aromatic hydrocarbon compound by using the ethanol, the selectivity of the aromatic hydrocarbon compound is more than 40%.
Alternatively, the selectivity to aromatic compounds is greater than 60%.
Preferably, the selectivity of the aromatic compounds is greater than 70%.
According to the method for preparing the aromatic hydrocarbon compound by using the ethanol, the BTX selectivity is more than 30 percent.
Alternatively, the BTX selectivity is greater than 55%.
Preferably, the BTX selectivity is greater than 65%.
In the present application, the term "aromatic hydrocarbon compound" refers to a hydrocarbon compound having a benzene ring structure.
"BTX" refers to a mixture of benzene-toluene-xylene.
The beneficial effects that this application can produce include:
1) according to the method for preparing the aromatic hydrocarbon compound by using the ethanol, the carbon monoxide is added in the ethanol aromatization reaction, so that the selectivity of the aromatic hydrocarbon, particularly BTX, can be improved and stabilized, and the one-way service life of the catalyst is prolonged.
2) According to the method for preparing the aromatic compound by using the ethanol, the performance of the catalyst subjected to ethanol aromatization inactivation in the carbon monoxide atmosphere is not obviously reduced after multiple regenerations.
3) According to the method for preparing the aromatic hydrocarbon compound by using the ethanol, the step of adding the metal auxiliary agent is omitted in the catalyst preparation process, and the process is simplified.
4) According to the method for preparing the aromatic hydrocarbon compound by using the ethanol, the catalyst does not need to be added with metal elements, so that the cost is greatly saved, and the method is beneficial to environmental protection.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with a gas autosampler, TCD detector connected to a TDX-1 packed column, and FID detector connected to a Plot-Q capillary column.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, both conversion and selectivity are calculated on a carbon mole basis:
ethanol conversion rate [ (moles of ethanol carbon in feed) - (moles of ethanol carbon in discharge) ] ÷ (moles of ethanol carbon in feed) × (100%)
Liquid hydrocarbon (hydrocarbons containing 5 carbons or more) selectivity (carbon mole number of liquid hydrocarbon in discharged material) ÷ (carbon mole number of all products in discharged material) × (100%)
Aromatic selectivity (carbon mole number of aromatic hydrocarbons in discharge) ÷ (carbon mole number of all products in discharge) × (100%)
BTX selectivity (moles of carbon BTX in the output) ÷ (moles of carbon of all products in the output) × (100%)
Testing of catalyst Performance
Example 1
Hydrogen type ZSM-5 molecular sieve (HZSM-5) (19) of 10g Si/Al-19 purchased from catalyst factory of southern Kai university) is tableted and sieved into particles of 20-40 meshes, and the particles are filled into the particles with the inner diameter of 16mmIn a stainless steel reaction tube, activating for 4h at 550 ℃ by using 100ml/min nitrogen, and reacting under the following conditions: the reaction temperature (T) is 350 ℃, the reaction pressure (P) is 0.5MPa, and the ethanol mass space velocity (WHSV) is 0.01h-1Carbon monoxide: ethanol (CO: EtOH) ═ 1: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 2
A hydrogen type ZSM-5 molecular sieve (HZSM-5) (200 for short) with the Si/Al of 10g and 200 purchased from catalyst factories of southern Kai university is tableted and sieved into particles with the meshes of 20-40, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 550 ℃, the reaction pressure (P) is 10MPa, and the ethanol mass space velocity (WHSV) is 20h-1Carbon monoxide: ethanol (CO: EtOH) ═ 100: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 3
A hydrogen type ZSM-5 molecular sieve with the Si/Al being 4, which is purchased from Shanghai Zhuoyue company, is abbreviated as HZSM-5(4), is tableted and sieved into particles with the granularity of 20-40 meshes, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min nitrogen and reacts under the following conditions: the reaction temperature (T) is 450 ℃, the reaction pressure (P) is 5MPa, and the ethanol mass space velocity (WHSV) is 2h-1Carbon monoxide: ethanol (CO: EtOH) ═ 40: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 4
A hydrogen type ZSM-5 molecular sieve with Si/Al of 70, HZSM-5(70) purchased from Shanghai Zhuoyue company, is tableted and sieved into particles with 20-40 meshes, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 5
A hydrogen ZSM-5 fraction of 10g Si/Al-40 from Shanghai Zuoyue was purchasedAnd (3) a sub-sieve, HZSM-5(40) for short, tabletting, sieving into particles of 20-40 meshes, filling into a stainless steel reaction tube with the inner diameter of 16mm, activating for 4 hours at 550 ℃ by using 100ml/min nitrogen, and reacting under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 6
A hydrogen type ZSM-5 molecular sieve (HZSM-5) (25 for short) with the Si/Al of 10g and 25 purchased from Oko corporation is tableted and sieved into particles with the meshes of 20-40, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 7
The preparation method comprises the following steps of tabletting 10g of hydrogen type ZSM-35 molecular sieve with Si/Al of 25, abbreviated as HZSM-35(25), which is purchased from catalyst factories of southern Kaiki university, sieving the powder into particles with 20-40 meshes, filling the particles into a stainless steel reaction tube with the inner diameter of 16mm, activating the particles for 4 hours at 550 ℃ by using 100ml/min of nitrogen, and reacting under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 8
A hydrogen type ZSM-5 molecular sieve with the Si/Al of 10g being 30 purchased from catalyst factories of southern Kai university, HZSM-5(30) for short, is tableted and sieved into particles with the mesh size of 20-40, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 9
The preparation method comprises the following steps of tabletting 10g of hydrogen type H-ZSM-35 molecular sieve (HZSM-35 (40) which is purchased from catalyst factories of southern Kai university and has Si/Al of 40), sieving the powder into particles with 20-40 meshes, filling the particles into a stainless steel reaction tube with the inner diameter of 16mm, activating the particles for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacting under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 10
A hydrogen MOR molecular sieve (MOR (20) with the Si/Al of 10g being 20 purchased from catalyst factories of southern Kai university) is tableted and sieved into particles with the meshes of 20-40, the particles are loaded into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Carbon monoxide: ethanol (CO: EtOH) ═ 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 1
A hydrogen type ZSM-5 molecular sieve with the Si/Al of 10g being 30 purchased from catalyst factories of southern Kai university, HZSM-5(30) for short, is tableted and sieved into particles with the mesh size of 20-40, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 3MPa, and the ethanol mass space velocity (WHSV) is 1h-1Nitrogen gas: ethanol (N)2EtOH) 20: 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 2
A hydrogen type ZSM-5 molecular sieve with the Si/Al of 10g being 30 purchased from catalyst factories of southern Kai university, HZSM-5(30) for short, is tableted and sieved into particles with the mesh size of 20-40, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 0.1MPa, and the ethanol mass space velocity (WHSV) is 1h-1Nitrogen gas: ethanol (N)2EtOH) 20: 1. Stable reactionAfter calibration, the product was analyzed by gas chromatography and the results are shown in Table 1.
Comparative example 3
A hydrogen type ZSM-5 molecular sieve with the Si/Al of 10g being 30 purchased from catalyst factories of southern Kai university, HZSM-5(30) for short, is tableted and sieved into particles with the mesh size of 20-40, the particles are put into a stainless steel reaction tube with the inner diameter of 16mm, and the stainless steel reaction tube is activated for 4 hours at the temperature of 550 ℃ by 100ml/min of nitrogen and reacts under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 0.1MPa, and the ethanol mass space velocity (WHSV) is 1h-1And no other carrier gas. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 4
The preparation method comprises the following steps of tabletting 10g of hydrogen type H-ZSM-35 molecular sieve (HZSM-35 (40) which is purchased from catalyst factories of southern Kai university and has Si/Al of 40), sieving the powder into particles with 20-40 meshes, filling the particles into a stainless steel reaction tube with the inner diameter of 16mm, activating the particles for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacting under the following conditions: the reaction temperature (T) is 400 ℃, the reaction pressure (P) is 0.1MPa, and the ethanol mass space velocity (WHSV) is 1h-1And no other carrier gas. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Table 1: results of catalytic reactions in examples 1 to 8 and comparative examples 1 to 4
As can be seen from Table 1, the addition of carbon monoxide in the ethanol aromatization reaction can improve and stabilize the selectivity of aromatics, particularly BTX, and prolong the one-way life of the catalyst. Meanwhile, the molecular sieve catalyst does not need to add metal elements in the process, so that the process is simplified, the cost is greatly saved, and the environment protection is facilitated.
Catalyst regeneration Performance test
Example 11
The deactivated catalyst in example 8 is treated at 550 ℃ for 10h by using a mixed gas of 2% by volume of oxygen and 98% by volume of nitrogen, so that the catalyst is regenerated and reacted under the conditions of example 8. Five rounds were repeated in the same manner, and the catalytic activity data after 20h of reaction for each round were selected for comparison, and the results are shown in table 2.
Comparative example 5
The HZSM-5(30) in the example 8 is dipped into zinc nitrate solution by an equal volume method, dried and calcined at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve with 2 percent of zinc content, which is abbreviated as Zn/HZSM-5(30), and the reaction is carried out under the condition of the example 8. Five rounds were repeated in the same manner, and the catalytic activity data after 20h of reaction for each round were selected for comparison, and the results are shown in table 2.
Table 2: results of catalytic reactions in example 9 and comparative example 4
As can be seen from Table 2, when the metal-modified molecular sieve is used in the process of adding carbon monoxide in the ethanol aromatization reaction, the aromatization performance of the catalyst after the regeneration treatment is obviously reduced; and the molecular sieve catalyst which does not need to be modified by a metal additive is used, so that the performance of the catalyst after the regeneration treatment is not obviously reduced, and the industrial utilization is facilitated.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing aromatic compounds from ethanol is characterized in that raw materials containing ethanol and carbon monoxide are in contact reaction with an acidic molecular sieve catalyst in a reaction zone to obtain aromatic compounds;
wherein the acidic molecular sieve catalyst does not contain a metal element.
2. The process according to claim 1, wherein the molar ratio of the carbon monoxide to the ethanol is not less than 1: 1;
preferably, the molar ratio of the carbon monoxide to the ethanol is 20: 1-100: 1.
3. The method of claim 1, wherein the acidic molecular sieve catalyst is selected from at least one of an RHO configuration acidic molecular sieve, a CHA configuration acidic molecular sieve, a FER configuration acidic molecular sieve, an MFI configuration acidic molecular sieve, an MOR configuration acidic molecular sieve, a FAU configuration acidic molecular sieve, and an EMT configuration acidic molecular sieve.
4. The process of claim 3, wherein the acidic molecular sieve catalyst is selected from at least one of a hydrogen form of ZSM-5 molecular sieve, a hydrogen form of ZSM-35 molecular sieve, and a hydrogen form of MOR molecular sieve.
5. The method of claim 1, wherein the acidic molecular sieve catalyst has an atomic ratio of silicon to aluminum of 3 to 200 Si/Al;
preferably, the atomic ratio of silicon to aluminum in the acidic molecular sieve catalyst is 10-40.
6. The method of claim 1, wherein the reaction conditions of the reaction are:
the reaction temperature is 350-550 ℃, and the reaction pressure is 0.5-10 MPa;
preferably, the reaction temperature is 390-480 ℃, and the reaction pressure is 3-7 MPa.
7. The method according to claim 1, wherein the mass space velocity of the ethanol is 0.01-20 h-1；
Preferably, the mass space velocity of the ethanol is 0.3-3 h-1。
8. The method of claim 1, wherein the acidic molecular sieve catalyst has a lifetime of 1000h or more after being subjected to a regeneration treatment.
9. The process of claim 1, wherein the reaction zone comprises one reactor or a plurality of reactors connected in series and/or parallel.
10. The method according to claim 9, characterized in that the reactor is a fixed bed reactor, a moving bed reactor or a fluidized bed reactor for carrying out a continuous reaction;
preferably, the reactor is a fixed bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232567.0A CN112920006A (en) | 2019-12-05 | 2019-12-05 | Method for preparing aromatic hydrocarbon compound from ethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232567.0A CN112920006A (en) | 2019-12-05 | 2019-12-05 | Method for preparing aromatic hydrocarbon compound from ethanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112920006A true CN112920006A (en) | 2021-06-08 |
Family
ID=76160916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911232567.0A Pending CN112920006A (en) | 2019-12-05 | 2019-12-05 | Method for preparing aromatic hydrocarbon compound from ethanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112920006A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024036466A1 (en) * | 2022-08-16 | 2024-02-22 | 中国科学院大连化学物理研究所 | Method for preparing aromatic hydrocarbons from methanol and/or dimethyl ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973679A (en) * | 2016-10-24 | 2018-05-01 | 中国科学院大连化学物理研究所 | A kind of method for preparing aromatic hydrocarbons |
-
2019
- 2019-12-05 CN CN201911232567.0A patent/CN112920006A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973679A (en) * | 2016-10-24 | 2018-05-01 | 中国科学院大连化学物理研究所 | A kind of method for preparing aromatic hydrocarbons |
Non-Patent Citations (1)
| Title |
|---|
| 时旭等: "醇原位催化转化制备芳烃及机理", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024036466A1 (en) * | 2022-08-16 | 2024-02-22 | 中国科学院大连化学物理研究所 | Method for preparing aromatic hydrocarbons from methanol and/or dimethyl ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2009215655B2 (en) | Process for the conversion of ethane to aromatic hydrocarbons | |
| US9144790B2 (en) | Process for the conversion of ethane to aromatic hydrocarbons | |
| US20140235911A1 (en) | Catalyst for the preparation of aromatic hydrocarbons and use thereof | |
| US20220111359A1 (en) | Catalyst for dehydrogenation of light alkanes | |
| RU2715244C1 (en) | Method of producing aromatic hydrocarbons | |
| AU2009235497B2 (en) | Method for the dehydroaromatisation of mixtures containing methane by regenerating the corresponding catalysts that are devoid of precious metal | |
| WO2009105391A1 (en) | Process for the conversion of ethane to aromatic hydrocarbons | |
| US20110257452A1 (en) | Regenerable Composite Catalysts for Hydrocarbon Aromatization | |
| SG185117A1 (en) | Methane aromatization catalyst, method of making and method of using the catalyst | |
| CN112920006A (en) | Method for preparing aromatic hydrocarbon compound from ethanol | |
| US20110253596A1 (en) | Regenerable Composite Catalysts for Paraffin Aromatization | |
| CN102950017B (en) | Oil refinery dry gas is utilized to produce the Catalysts and its preparation method of gasoline | |
| WO2011143306A2 (en) | Process for the conversion of lower alkanes to aromatic hydrocarbons | |
| US20160368836A1 (en) | Process for the aromatization of a methane-containing gas stream using zirconium hydrogen acceptor particles | |
| CN112920011A (en) | Method for preparing aromatic hydrocarbon compound from methanol | |
| CN112745189A (en) | Method for producing aromatic hydrocarbon by carbonylation of normal hexane | |
| CN114573413B (en) | Method for generating aromatic hydrocarbon by coupling alkane and carbon monoxide | |
| CN117736063A (en) | Method for preparing aromatic hydrocarbon from low-carbon alkane | |
| US20230249163A1 (en) | Catalyst system and light hydrocarbon aromatization method, carbon dioxide hydrogenation process and method for enhancing catalyst lifetime | |
| CN112439447B (en) | Heavy aromatic hydrocarbon lightening catalyst and preparation method and application thereof | |
| WO2023003624A1 (en) | Catalyst and process for conversion of c2-c5 alkanes to gasoline blending components | |
| US20110160507A1 (en) | Method for obtaining aromatic hydrocarbons from methane | |
| CN117623841A (en) | Method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether | |
| WO2013102475A1 (en) | Catalyst for the preparation of aromatic hydrocarbons and use thereof | |
| JP2020196685A (en) | Catalyst system for benzene production and method for producing benzene using the same |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210608 |
|
| RJ01 | Rejection of invention patent application after publication |