CN111253199B - Method for preparing ethylene by ethanol dehydration - Google Patents

Method for preparing ethylene by ethanol dehydration Download PDF

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CN111253199B
CN111253199B CN201811458081.4A CN201811458081A CN111253199B CN 111253199 B CN111253199 B CN 111253199B CN 201811458081 A CN201811458081 A CN 201811458081A CN 111253199 B CN111253199 B CN 111253199B
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catalyst
molecular sieve
reaction
mordenite molecular
solution
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CN111253199A (en
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郅玉春
魏迎旭
刘中民
林杉帆
王男
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The application discloses a method for preparing ethylene by ethanol dehydration, which is characterized in that raw materials containing ethanol pass through a reactor filled with a catalyst to be in contact reaction with the catalyst to generate products containing ethylene; the reaction conditions are as follows: the reaction temperature is 200-400 ℃, the reaction pressure is 0-2 MPa, and the mass airspeed of ethanol is 0.1-15 h‑1(ii) a The catalyst is a mordenite molecular sieve subjected to dealumination treatment. The catalyst used in the method is a mordenite molecular sieve for selectively removing 12-membered ring channel framework aluminum. The modified mordenite molecular sieve is used for catalyzing the reaction of preparing ethylene by ethanol dehydration, has excellent reaction activity under the condition of low temperature, and has the reaction temperature of 220 ℃ and the airspeed of up to 6h‑1Under the reaction conditions of (1), the conversion rate of the ethanol is 100 percent, and the selectivity of the ethylene is up to 99 percent.

Description

Method for preparing ethylene by ethanol dehydration
Technical Field
The application relates to a method for preparing ethylene by ethanol dehydration, in particular to a method for preparing ethylene by ethanol dehydration by taking an H-type mordenite molecular sieve for selectively removing 12-membered ring channel framework aluminum as a catalyst, belonging to the field of catalytic chemical engineering.
Background
Ethylene is the most basic chemical feedstock, with about 75% of the petrochemical products being derived from ethylene. The scale, yield and technology of industrial production of ethylene have become an important marker for the state development of the chemical industry. At present, the preparation of ethylene from petroleum is still the most advantageous and perfect industrial production route, but the reaction temperature is usually as high as 850 ℃, the energy consumption is large, and with the increasing exhaustion of petroleum resources, the ethylene industry using petroleum as raw material is bound to be greatly impacted. The method for preparing ethylene by using renewable biomass resources to obtain ethanol is also an inevitable trend and conforms to the strategy of sustainable development. In addition, the existing coal chemical technology in China is developed more mature, the route of the coal for preparing ethanol from methanol and then preparing ethylene meets the future domestic market demand, and the competitive advantage is obvious.
The high-efficiency catalyst is one of the key technologies for preparing ethylene by ethanol dehydration. Ethanol dehydration catalysts reported in industrial applications fall into two main categories, namely, activated alumina catalysts and molecular sieve catalysts.
Currently, activated alumina remains the predominant commercially available catalyst. The industrial reaction parameters of the activated alumina catalyst are summarized in "chemical evolution" 2006, volume 25, phase 8: the reaction temperature is 350-450 ℃, and the airspeed is 0.2-0.8 h-1The conversion per pass of the ethanol is 92-97 percent, and the selectivity of the ethylene is 95-97 percent. The catalyst has high reaction temperature and low space velocity, which leads to higher energy consumption and lower equipment utilization rate in industrial application.
Patents EP0022640, US4698452, US4873392 found that molecular sieve catalysts have lower reaction temperature, higher operating space velocity and higher per pass reaction conversion and ethylene yield than alumina catalysts in ethanol dehydration reactions. Especially, the ZSM-5 molecular sieve catalyst has more advantages in the aspect of catalytic dehydration performance because of oleophylic and hydrophobic properties. The reaction temperature is 250-300 ℃, and the airspeed is 1-2 h-1Ethanol conversion rate greater than 99.5%, ethylene selectivity greater than 99%, specific activity Al2O3The catalyst is greatly improved. However, the reaction temperature of the prior molecular sieve catalyst such as ZSM-5 and the like is still high, the space velocity is still low, the magnification is small, and the industrial development of the molecular sieve catalyst is limited.
Disclosure of Invention
According to one aspect of the application, the method for preparing the ethylene by ethanol dehydration is provided, and the method overcomes the problems of high reaction temperature, low space velocity, high energy consumption and the like in the prior art. The method can realize the high-efficiency dehydration of the ethanol to prepare the ethylene under the conditions of lower temperature and higher airspeed.
The method for preparing the ethylene by ethanol dehydration is characterized in that a raw material containing the ethanol passes through a reactor filled with a catalyst to contact and react with the catalyst to generate a product containing the ethylene; the reaction conditions are as follows: the reaction temperature is 200-400 ℃, the reaction pressure is 0-2 MPa, and the mass airspeed of ethanol is 0.1-15 h-1；
The catalyst is a mordenite molecular sieve subjected to dealumination treatment.
Optionally, the upper limit of the reaction temperature is selected from 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃; the lower limit is selected from 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 300 deg.C or 350 deg.C.
Optionally, the upper limit of the reaction pressure is selected from 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.5MPa or 2 MPa; the lower limit is selected from 0MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa or 1.5 MPa.
Alternatively, the upper limit of the ethanol mass space velocity is selected from 0.2h-1、0.5h-1、1h-1、1.5h-1、2h-1、3h-1、4h-1、5h-1、6h-1、8h-1、10h-1、12h-1Or 15h-1Starting the process; the lower limit is selected from 0.1h-1、0.2h-1、0.5h-1、1h-1、1.5h-1、2h-1、3h-1、4h-1、5h-1、6h-1、8h-1、10h-1Or 12h-1。
The treatment method can selectively remove the acid sites of the 12-membered ring channels of the mordenite molecular sieve and reserve the acid sites of the 8-membered ring channels. The unique channel structure of the 8-membered ring and the space confinement effect thereof can obviously improve the reaction activity of preparing ethylene by ethanol dehydration, effectively inhibit secondary reaction and improve the selectivity of ethylene.
Specifically, the method for preparing ethylene by ethanol dehydration comprises the step of enabling raw material ethanol to pass through a reactor filled with a catalyst to contact with the catalyst to generate ethylene, wherein the catalystThe catalyst is an H-type mordenite molecular sieve for selectively removing 12-membered ring channel framework aluminum, the raw material is ethanol, the reaction conditions are that the reaction temperature is 200-400 ℃, the reaction pressure is 0-2 MPa, and the mass airspeed of the ethanol is 0.1-15H-1。
Alternatively, the catalyst is a mordenite molecular sieve depleted of framework aluminum in 12-membered ring channel.
Alternatively, the catalyst is a hydrogen mordenite molecular sieve with 12-membered channel framework aluminum removed.
Specifically, the catalyst is an H-type mordenite molecular sieve for selectively removing 12-membered ring channel framework aluminum.
Optionally, the mordenite molecular sieve has a silicon-aluminum ratio Si/Al molar ratio of 5-80.
Optionally, the mordenite molecular sieve has a silicon-aluminum (Si/Al) molar ratio of 5-50;
wherein the mole number of Si is calculated as the mole number of Si element, and the mole number of Al is calculated as the mole number of Al element.
Optionally, the mordenite molecular sieve has an upper limit on the silicon to aluminum Si/Al molar ratio selected from 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 18, 20, 25, 30, 40, 50, 60, 70 or 80; the lower limit is selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 18, 20, 25, 30, 40, 50, 60 or 70.
Specifically, the silicon-aluminum ratio of the H-type mordenite molecular sieve catalyst ranges from 5 to 80.
Alternatively, the conditions of the reaction: the reaction temperature is 200-250 ℃, the reaction pressure is 0.1-1 MPa, and the mass space velocity of ethanol is 0.5-10 h-1。
Optionally, the preparation method of the catalyst comprises the following steps:
(a11) placing the mordenite molecular sieve in an alkali solution, and stirring at room temperature for 0.1-3 h;
(a12) treating the mordenite molecular sieve treated in the step (a11) for 2-10 h at 600-1000 ℃ in a water vapor-containing atmosphere;
(a13) placing the mordenite molecular sieve treated in the step (a12) in 0.1-2M NH4NO3And stirring the solution at room temperature for 5-15 h, washing and drying, and calcining the solution at 400-600 ℃ in the air atmosphere for 5-10 h to obtain the catalyst.
Optionally, step (a11) is: and (3) placing the hydrogen mordenite molecular sieve in 0.001-0.5M NaOH solution, and stirring at room temperature for 0.1-3 h.
Alternatively, the upper limit of the concentration of the NaOH solution in step (a11) is selected from 0.005M, 0.01M, 0.05M, 0.1M, 0.2M, 0.3M, 0.4M or 0.5M; the lower limit is selected from 0.001M, 0.005M, 0.01M, 0.05M, 0.1M, 0.2M, 0.3M or 0.4M.
Optionally, the upper limit of the time of the stirring treatment in step (a11) is selected from 0.3h, 0.5h, 0.8h, 1h, 2h or 3 h; the lower limit is selected from 0.1h, 0.3h, 0.5h, 0.8h, 1h or 2 h.
Optionally, step (a12) is: statically treating the mordenite molecular sieve treated in the step (a11) for 2-10 h at 600-1000 ℃ in a water vapor-containing atmosphere; the water vapor-containing atmosphere is a mixed gas of water vapor and an inactive gas; the inactive gas is at least one of nitrogen and inert gas.
Optionally, the upper limit of the temperature of the static treatment under a water vapor-containing atmosphere in step (a12) is selected from 700 ℃, 800 ℃, 900 ℃ or 1000 ℃; the lower limit is selected from 600 deg.C, 700 deg.C, 800 deg.C or 900 deg.C.
Optionally, the upper limit of the time of the static treatment under a water vapor-containing atmosphere in step (a12) is selected from 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h; the lower limit is selected from 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9 h.
Optionally, the NH of step (a13)4NO3The upper limit of the concentration of the solution is selected from 0.2M, 0.5M, 0.8M, 1M, 1.5M or 2M; the lower limit is selected from 0.1M, 0.2M, 0.5M, 0.8M, 1M or 1.5M.
Optionally, the upper time limit of the stirring treatment in step (a13) is selected from 8h, 10h, 12h or 15 h; the lower limit is selected from 5h, 8h, 10h or 12 h.
Alternatively, the upper limit of the temperature of the calcination in step (a13) is selected from 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the lower limit is selected from 400 deg.C, 450 deg.C, 500 deg.C or 550 deg.C.
Alternatively, the upper limit of the time of the calcination in step (a13) is selected from 6h, 7h, 8h, 9h, or 10 h; the lower limit is selected from 5h, 6h, 7h, 8h or 9 h.
Optionally, the water vapor-containing atmosphere is a mixed gas of water vapor and nitrogen; the volume fraction of the water vapor in the water vapor-containing atmosphere is 0.1-50%.
Optionally, the water vapor-containing atmosphere is a mixed gas of water vapor and nitrogen; the volume fraction of water vapor in the water vapor-containing atmosphere was 30%.
Optionally, the preparation method of the catalyst comprises the following steps:
(a21) placing the mordenite molecular sieve in an alkali solution, and stirring at room temperature for 0.1-3 h;
(a22) placing the mordenite molecular sieve treated in the step (a21) in 0.1-2M organic acid-containing solution, mineral acid-containing solution or fluorine-containing salt solution, and stirring for 2-15 h;
(a23) placing the mordenite molecular sieve treated in the step (a22) in 0.1-2M NH4NO3And stirring the solution at room temperature for 5-15 h, washing and drying, and calcining the solution at 400-600 ℃ in the air atmosphere for 5-10 h to obtain the catalyst.
Optionally, the step (a21) is: and (3) placing the hydrogen mordenite molecular sieve in 0.001-0.5M NaOH solution, and stirring at room temperature for 0.1-3 h.
Alternatively, the upper limit of the concentration of the NaOH solution in step (a21) is selected from 0.005M, 0.01M, 0.05M, 0.1M, 0.2M, 0.3M, 0.4M or 0.5M; the lower limit is selected from 0.001M, 0.005M, 0.01M, 0.05M, 0.1M, 0.2M, 0.3M or 0.4M.
Optionally, the upper limit of the time of the stirring treatment in step (a21) is selected from 0.3h, 0.5h, 0.8h, 1h, 2h or 3 h; the lower limit is selected from 0.1h, 0.3h, 0.5h, 0.8h, 1h or 2 h.
Optionally, the organic acid in step (a22) is selected from at least one of oxalic acid, acetic acid, citric acid;
the mineral acid is at least one of nitric acid, hydrochloric acid and hydrofluoric acid;
the fluorine-containing salt is selected from at least one of ammonium fluoride and ammonium fluorosilicate.
Optionally, the NH of step (a23)4NO3The upper limit of the concentration of the solution is selected from 0.2M, 0.5M, 0.8M, 1M, 1.5M or 2M; the lower limit is selected from 0.1M, 0.2M, 0.5M, 0.8M, 1M or 1.5M.
Optionally, the NH of step (a23)4NO3The upper limit of the concentration of the solution is selected from 0.2M, 0.5M, 0.8M, 1M, 1.5M or 2M; the lower limit is selected from 0.1M, 0.2M, 0.5M, 0.8M, 1M or 1.5M.
Optionally, the upper time limit of the stirring treatment in step (a23) is selected from 8h, 10h, 12h or 15 h; the lower limit is selected from 5h, 8h, 10h or 12 h.
Alternatively, the upper limit of the temperature of the calcination in step (a23) is selected from 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the lower limit is selected from 400 deg.C, 450 deg.C, 500 deg.C or 550 deg.C.
Alternatively, the upper limit of the time of the calcination in step (a23) is selected from 6h, 7h, 8h, 9h, or 10 h; the lower limit is selected from 5h, 6h, 7h, 8h or 9 h.
Specifically, the catalyst modification preparation process comprises the following steps:
(1) placing the H-type mordenite molecular sieve with completely removed adsorbed water in 0.001-0.5M NaOH dilute solution, stirring at room temperature for 0.1-3H, and selectively substituting acidic protons in 8-membered ring channels of the molecular sieve with sodium ions;
(2) subjecting the molecular sieve treated in the step (1) to high temperature of 600-1000 ℃, and in a water vapor atmosphere with a volume ratio of 0-100 (N)2Balance gas) for 2-10 h, and removing framework aluminum of 12-membered ring channels of the molecular sieve; or placing the catalyst treated in the step (1) in 0.1-2M organic acid, mineral acid or fluorine-containing salt solution, stirring for 2-15 h, and removing framework aluminum of the 12-membered ring channel;
(3) placing the molecular sieve treated in the step (2) in 0.1-2M NH4NO3Stirring the solution at room temperature for 5-15H, washing and drying, and calcining at 400-600 ℃ in air for 5-10H to obtain the H-type mordenite molecular sieve catalyst for selectively removing the 12-membered ring channel framework aluminum.
The organic acid is at least one of oxalic acid, acetic acid and citric acid.
The mineral acid is at least one selected from nitric acid, hydrochloric acid and hydrofluoric acid.
The fluorine-containing salt is selected from at least one of ammonium fluoride and ammonium fluorosilicate.
As an embodiment, the catalyst modification preparation process in the above technical scheme is: placing the H-type mordenite molecular sieve with completely removed adsorbed water in 0.001-0.5M NaOH dilute solution, stirring at room temperature for 0.1-3H, and selectively substituting acidic protons in 8-membered ring channels of the molecular sieve with sodium ions. Then, the catalyst is heated at a high temperature of 600-1000 ℃ in a water vapor atmosphere (N) with a volume ratio of 0-1002Balance gas) for 2-10 h, and removing framework aluminum of 12-membered ring channels of the molecular sieve; or placing the catalyst in 0.1-2M organic acid, mineral acid or fluorine-containing salt solution, and stirring for 2-15 h to remove the framework aluminum of the 12-membered ring channel. Then, the catalyst is placed in 0.1-2M NH4NO3And stirring the solution at room temperature for 5-15H, washing and drying the solution, and calcining the solution at 400-600 ℃ in air for 5-10H to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum.
Optionally, the reactor is a fixed bed and/or a fluidized bed reactor.
Optionally, the catalyst is dealuminated prior to passing the ethanol-containing feedstock to the reactor containing the catalyst.
The beneficial effects that this application can produce include:
1) the method for preparing ethylene by ethanol dehydration provided by the application and the current industrial Al2O3Compared with the catalyst, the reaction temperature is reduced from 350-450 ℃ to about 220 ℃; the reaction temperature is greatly reduced, so that the reaction energy consumption can be obviously reduced, and some side reactions possibly occurring in the catalytic dehydration reaction process of the ethanol, such as the reaction for generating ethyl ether, high-carbon olefin and the like, are reduced, and finally the improvement of the selectivity of the ethylene is facilitated. In addition, the lower reaction temperature can reduce the carbon deposition rate of the catalyst and effectively prolong the service life of the catalyst;
2) b provided by the present applicationThe catalyst adopts H-type mordenite molecular sieve for selectively removing 12-membered ring channel framework aluminum, so that the reaction can be carried out for 6H-1The method is carried out under the condition of high airspeed, thereby greatly improving the production capacity of a unit device and greatly improving the production benefit;
3) according to the method for preparing ethylene by ethanol dehydration, the ethanol conversion rate can reach 100%, and the ethylene selectivity can reach 99%.
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 starting materials and catalysts in the examples of this application were purchased commercially, with mordenite molecular sieves purchased from southern university catalyst factories.
The analysis method in the examples of the present application is as follows:
analysis of the reaction product was performed by GC-MS.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, both ethanol conversion and ethylene selectivity were calculated based on carbon moles.
Example 1
Placing the H-type mordenite molecular sieve (the Si/Al ratio is 15) which is completely removed by the absorbed water into 0.01M NaOH dilute solution, stirring at room temperature for 1H, and selectively substituting the acidic proton of the 8-membered ring channel of the molecular sieve by sodium ion. Thereafter, the catalyst was heated at a high temperature of 800 ℃ under a steam atmosphere (N) at a volume ratio of 302Is balance gas) for 6 hours, and framework aluminum of 12-membered ring channels of the molecular sieve is removed. Thereafter, the catalyst was placed in 1M NH4NO3Stirring the solution at room temperature for 10H, washing and drying the solution, and calcining the solution at 500 ℃ in air for 5H to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum.
The performance evaluation of the catalyst was carried out on a fixed-bed reactor at atmospheric pressure, using a quartz tube fixed-bed reactor having an inner diameter of 6 mm. The reaction temperature is 220 ℃, the reaction pressure is 0.1MPa, and the mass airspeed of the ethanol isIs 6h-1. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 2
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction temperature was 300 ℃, and the other reaction conditions were unchanged. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 3
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction temperature was 350 ℃, and the other reaction conditions were unchanged. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 4
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction pressure was 0.4MPa, and the other reaction conditions were not changed. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 5
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction pressure was 1MPa, and the other reaction conditions were not changed. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 6
The catalyst in the embodiment 1 is selected, the treatment condition is not changed, and the methanol mass space velocity for evaluating the performance of the catalyst is 2h-1The other reaction conditions were unchanged. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 7
Placing the H-type mordenite molecular sieve (the Si/Al ratio is 15) which is completely removed by the absorbed water into 0.01M NaOH dilute solution, stirring at room temperature for 1H, and selectively substituting the acidic proton of the 8-membered ring channel of the molecular sieve by sodium ion. And then, placing the catalyst in a 1M oxalic acid solution, stirring and treating for 10 hours, and removing framework aluminum of 12-membered ring channels of the molecular sieve. Thereafter, the catalyst was placed in 1M NH4NO3Stirring the solution at room temperature for 10H, washing and drying the solution, and calcining the solution at 500 ℃ in air for 5H to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum.
The catalyst performance evaluation conditions were the same as in example 1, and the reaction results are shown in Table 1.
Example 8
The catalyst treatment conditions in example 4 were selected to be unchanged, the catalyst performance evaluation reaction temperature was 300 ℃, and the other reaction conditions were unchanged. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1.
Example 9
Placing the H-type mordenite molecular sieve (the Si/Al ratio is 15) which is completely removed by the absorbed water into 0.01M NaOH dilute solution, stirring at room temperature for 1H, and selectively substituting the acidic proton of the 8-membered ring channel of the molecular sieve by sodium ion. And then, placing the catalyst in a 1.5M nitric acid solution, stirring and treating for 12 hours, and removing framework aluminum of 12-membered ring channels of the molecular sieve. Thereafter, the catalyst was placed in 1M NH4NO3Stirring the solution at room temperature for 10H, washing and drying the solution, and calcining the solution at 500 ℃ in air for 5H to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum.
The catalyst performance evaluation conditions were the same as in example 1, and the reaction results are shown in Table 1.
Example 10
Placing the H-type mordenite molecular sieve (the Si/Al ratio is 15) which is completely removed by the absorbed water into 0.01M NaOH dilute solution, stirring at room temperature for 1H, and selectively substituting the acidic proton of the 8-membered ring channel of the molecular sieve by sodium ion. And then, placing the catalyst in 1.5M ammonium fluosilicate solution, stirring and treating for 15h, and removing framework aluminum of 12-membered ring channels of the molecular sieve. Thereafter, the catalyst was placed in 1M NH4NO3Stirring the solution at room temperature for 10H, washing and drying the solution, and calcining the solution at 500 ℃ in air for 5H to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum.
The catalyst performance evaluation conditions were the same as in example 1, and the reaction results are shown in Table 1.
Example 11
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction temperature was 200 ℃, and the other reaction conditions were unchanged. The reaction product was analyzed by on-line GC-MS and the reaction result was similar to that of example 1.
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction temperature was 400 ℃, and the other reaction conditions were unchanged. The reaction product was analyzed by on-line GC-MS and the reaction result was similar to that of example 1.
The catalyst treatment conditions in example 1 were selected to be unchanged, and the catalyst performance evaluation mass space velocity was 0.1h-1The other reaction conditions were unchanged. The reaction product was analyzed by on-line GC-MS and the reaction result was similar to that of example 1.
The catalyst treatment conditions in example 1 were selected to be unchanged, and the catalyst performance evaluation mass space velocity was 10h-1The other reaction conditions were unchanged. The reaction product was analyzed by on-line GC-MS and the reaction result was similar to that of example 1.
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction pressure was MPa, and the other reaction conditions were not changed. The reaction product was analyzed by on-line GC-MS and the reaction result was similar to that of example 1.
The catalyst treatment conditions in example 1 were selected to be unchanged, the catalyst performance evaluation reaction pressure was 2MPa, and the other reaction conditions were not changed. The reaction product was analyzed by on-line GC-MS and the reaction result was similar to that of example 1.
The operation of catalyst treatment is the same as example 1, except that the H-type mordenite molecular sieve with completely removed adsorbed water is placed in 0.001M NaOH dilute solution and stirred at room temperature for 3H, the performance evaluation conditions of the catalyst are the same as example 1, and the reaction result is similar to example 1.
The catalyst treatment operation is the same as that in example 1, except that the H-type mordenite molecular sieve with completely removed adsorbed water is placed in 0.5M NaOH dilute solution and stirred for 1H at room temperature, the performance evaluation conditions of the catalyst are the same as those in example 1, and the reaction result is similar to that in example 1.
The catalyst treatment operation is the same as that in example 1, except that after the molecular sieve is treated by the dilute NaOH solution, the catalyst is statically treated for 2 hours at the high temperature of 600 ℃ in the steam atmosphere, framework aluminum of 12-membered ring channels of the molecular sieve is removed, the performance evaluation conditions of the catalyst are the same as those in example 1, and the reaction result is similar to that in example 1.
The catalyst treatment operation was the same as in example 1 except that the catalyst treatment was carried out in a water vapor atmosphere (N) at a volume ratio of 302Is balance gas) for 10 hours, framework aluminum of 12-membered ring channels of the molecular sieve is removed, the performance evaluation conditions of the catalyst are consistent with those of the catalyst in the example 1, and the reaction result is similar to that of the catalyst in the example 1.
The catalyst treatment operation was the same as in example 1 except that the catalyst was placed in 0.1M NH4NO3Stirring the solution at room temperature for 15H, washing and drying the solution, and calcining the solution at 400 ℃ in air for 10H to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum, wherein the performance evaluation conditions of the catalyst are the same as those of the example 1, and the reaction result is similar to that of the example 1.
The catalyst treatment operation was the same as in example 1 except that the catalyst was placed in 2M NH4NO3Stirring the solution at room temperature for 5 hours, washing and drying the solution, and calcining the solution at 600 ℃ in air for 5 hours to obtain the H-type mordenite molecular sieve for selectively removing the 12-membered ring channel framework aluminum, wherein the performance evaluation conditions of the catalyst are the same as those of the example 1, and the reaction result is similar to that of the example 1.
The catalyst treatment was carried out in the same manner as in example 7 except that the catalyst was stirred in a 0.1M oxalic acid solution for 15 hours, the conditions for evaluating the performance of the catalyst were the same as those in example 7, and the reaction results were similar to those in example 7.
The catalyst treatment was carried out in the same manner as in example 7 except that the catalyst was stirred in a 2M oxalic acid solution for 2 hours, the conditions for evaluating the performance of the catalyst were the same as those in example 7, and the reaction results were similar to those in example 7.
The catalyst treatment operation was the same as in example 1 except that an H-type mordenite molecular sieve having a silica-alumina ratio of 50 was used, the catalyst performance evaluation conditions were the same as in example 1, and the reaction results were similar to those in example 1.
The catalyst treatment operation was the same as in example 1 except that an H-type mordenite molecular sieve having a silica-alumina ratio of 80 was used, the catalyst performance evaluation conditions were the same as in example 1, and the reaction results were similar to those in example 1.
The catalyst treatment was carried out in the same manner as in example 1, zoneIs different in that2The catalyst is treated for 4 hours at the temperature of 350 ℃ under the atmosphere, then the temperature is reduced to 150 ℃, the performance evaluation conditions of the catalyst are consistent with those of the example 1, and the reaction result is similar to that of the example 1.
The catalyst treatment was carried out in the same manner as in example 1 except that the treatment was carried out at a temperature of 500 ℃ for 1 hour under an Ar atmosphere and then the temperature was lowered to 450 ℃ under the same catalyst performance evaluation conditions as in example 1, and the reaction results were similar to those in example 1.
The catalyst treatment operation was the same as in example 1, except that in N2Treating at 450 deg.C for 2h under atmosphere, cooling to 250 deg.C, introducing N2Adsorbing with saturated pyridine vapor for 12h, and then using N at 250 deg.C2Purging for 4H to obtain the saturated adsorbed H-type mordenite molecular sieve, wherein the performance evaluation conditions of the catalyst are the same as those of example 1, and the reaction result is similar to that of example 1.
The catalyst treatment operation was the same as in example 1, except that in N2Treating at 450 deg.C for 2h under atmosphere, cooling to 350 deg.C, introducing N2Adsorbing with saturated pyridine vapor for 1 hr, and adding N at 350 deg.C2Purging for 1H to obtain the saturated adsorbed H-type mordenite molecular sieve, wherein the performance evaluation conditions of the catalyst are the same as those of example 1, and the reaction result is similar to that of example 1.
Comparative example 1
A certain amount of a commercially available H-type mordenite molecular sieve with the silicon-aluminum ratio of 15 is subjected to performance evaluation of a catalyst on a normal-pressure fixed bed reaction device, and a quartz tube fixed bed reactor with the inner diameter of 6mm is adopted. In N2Pre-treatment for 2h at 450 ℃ under atmosphere. The reaction temperature is 220 ℃, the reaction pressure is 0.1MPa, and the mass space velocity of the ethanol is 6h-1. The reaction products were analyzed by on-line GC-MS and the results are shown in Table 1. Table 1 shows that the olefins prepared by ethanol dehydration in examples 1-11 all have 100% conversion and the ethylene selectivity is as high as 94.3-99.3%; the ethylene selectivity in comparative example 1 of the catalyst without organic amine modification was only 85%.
Table 1 evaluation results of examples
Conversion rate of ethanol% Ethylene selectivity%
Example 1 100 99.2
Example 2 100 98.6
Example 3 100 96.3
Example 4 100 99.1
Example 5 100 98.4
Example 6 100 99.3
Example 7 100 99.2
Example 8 100 94.2
Example 9 100 99.1
Example 10 100 99.2
Comparative example 1 100 85
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 (13)

1. A method for preparing ethylene by ethanol dehydration is characterized in that a raw material containing ethanol passes through a reactor filled with a catalyst to contact and react with the catalyst to generate a product containing ethylene; the reaction conditions are as follows: the reaction temperature is 200-350 ℃, the reaction pressure is 0.1-2 MPa, and the mass space velocity of ethanol is 0.1-15 h-1；
The catalyst is a hydrogen-type mordenite molecular sieve which removes 12-membered channel framework aluminum, selectively removes acid sites of 12-membered ring channels of the mordenite molecular sieve and reserves acid sites of 8-membered ring channels.
2. The method according to claim 1, wherein the mordenite molecular sieve has a silica-alumina ratio Si/Al molar ratio of 5 to 80;
wherein the mole number of Si is calculated as the mole number of Si element, and the mole number of Al is calculated as the mole number of Al element.
3. The method according to claim 1, wherein the mordenite molecular sieve has a Si/Al molar ratio of 5 to 50;
wherein the mole number of Si is calculated as the mole number of Si element, and the mole number of Al is calculated as the mole number of Al element.
4. The process according to claim 1, characterized in that the reaction conditions are: the reaction temperature is 200-250 ℃, the reaction pressure is 0.1-1 MPa, and the mass space velocity of ethanol is 0.5-10 h-1。
5. The method of claim 1, wherein the catalyst is prepared by a method comprising the steps of:
(a11) putting the hydrogen mordenite molecular sieve into an alkali solution, and stirring at room temperature for 0.1-3 h;
(a12) treating the mordenite molecular sieve treated in the step (a11) for 2-10 h at 600-1000 ℃ in a water vapor-containing atmosphere;
(a13) placing the mordenite molecular sieve treated in the step (a12) in 0.1-2M NH4NO3And stirring the solution at room temperature for 5-15 h, washing and drying, and calcining the solution at 400-600 ℃ in the air atmosphere for 5-10 h to obtain the catalyst.
6. The method of claim 5, wherein step (a11) is: and (3) placing the hydrogen mordenite molecular sieve in 0.001-0.5M NaOH solution, and stirring at room temperature for 0.1-3 h.
7. The method of claim 5, wherein step (a12) is: statically treating the mordenite molecular sieve treated in the step (a11) for 2-10 h at 600-1000 ℃ in a water vapor-containing atmosphere; the water vapor-containing atmosphere is a mixed gas of water vapor and an inactive gas; the inactive gas is at least one of nitrogen and inert gas.
8. The method of claim 5, wherein the water vapor-containing atmosphere is a mixed gas of water vapor and nitrogen gas; the volume fraction of the water vapor in the water vapor-containing atmosphere is 0.1-50%.
9. The method of claim 1, wherein the catalyst is prepared by a method comprising the steps of:
(a21) putting the hydrogen mordenite molecular sieve into an alkali solution, and stirring at room temperature for 0.1-3 h;
(a22) placing the mordenite molecular sieve treated in the step (a21) in 0.1-2M organic acid-containing solution, mineral acid-containing solution or fluorine-containing salt solution, and stirring for 2-15 h;
(a23) placing the mordenite molecular sieve treated in the step (a22) in 0.1-2M NH4NO3And stirring the solution at room temperature for 5-15 h, washing and drying, and calcining the solution at 400-600 ℃ in the air atmosphere for 5-10 h to obtain the catalyst.
10. The method of claim 9, wherein step (a21) is: and (3) placing the hydrogen mordenite molecular sieve in 0.001-0.5M NaOH solution, and stirring at room temperature for 0.1-3 h.
11. The method according to claim 9, wherein the organic acid in step (a22) is selected from at least one of oxalic acid, acetic acid, citric acid;
the mineral acid is at least one of nitric acid, hydrochloric acid and hydrofluoric acid;
the fluorine-containing salt is selected from at least one of ammonium fluoride and ammonium fluosilicate.
12. The process of claim 1, wherein the reactor is a fixed bed or a fluidized bed reactor.
13. The process of claim 1, wherein the catalyst is dealuminated prior to passing the ethanol-containing feedstock to the reactor containing the catalyst.
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