CN104820060B - Method for rapidly screening high-selectivity methanol-to-olefin catalyst - Google Patents
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Abstract
A method for rapidly screening a high-selectivity methanol-to-olefin catalyst comprises the steps of filling catalyst powder into a reactor, and filling inert silicon carbide particles on the upper part and the lower part of the reactor; the reactor is evacuated and then heated to 50-300 ℃ at a rate of 5-30 ℃/min. The mixed gases of ethylene/inert gas and propylene/inert gas with the volume ratio ranging from (20/80) to (80/20) are respectively injected into the reactor in a pulse mode, the residence time of the ethylene and the propylene in the bed layer of the reactor is measured, and the average diolefin selectivity of the catalyst is judged by the residence time. The method has the advantages of simple operation, short time and high accuracy.
Description
Technical Field
The invention relates to a method for rapidly screening a methanol-to-olefin catalyst with high diene selectivity.
Technical Field
The demand of low-carbon olefins, namely ethylene and propylene, which are two important basic chemical materials in modern industrial society will keep continuously increasing. Methanol To Olefin (MTO) is a chemical technology for producing low-carbon olefins by using Methanol synthesized from coal or natural gas as a raw material and using a catalyst. The key of the technology for preparing olefin from methanol is to develop a catalyst with high activity, good selectivity and high stability. At present, ZSM-5 and SAPO-34 molecular sieves are mainly used as catalysts for preparing olefin from methanol.
US6,087,180 discloses a technique for studying the mechanism of gas-solid phase interaction (temporalalanalysis of Products, TAP for short). TAP is an impulse response experimental method for exposing probe molecules (e.g., reactants, intermediates, products, or other species) to complex catalyst surfaces to reveal the chemical/kinetic state of the surface. The adsorption/desorption rate constants, the number and distribution of active sites, the number of surface species, the surface-to-bulk exchange kinetics and porous transport processes, etc. can be measured using TAP technology.
Morgan et al studied Au/CuMnO using TAP techniquexThe mechanism of the catalytic carbon monoxide oxidation reaction is that carbon monoxide and oxygen are used for carrying out a multi-pulse TAP experiment, and the gold (Au) can modify the surface of the catalyst to be beneficial to storing active oxygen for the reaction. Schuurman et al studied the transfer and adsorption of carbon deposits on catalytic cracking (FCC) catalysts using toluene as a probe molecule and found that when the amount of carbon deposits is low: (<2.6 wt%), the adsorption enthalpy of toluene rapidly decreases with increasing amount of soot, indicating that the most acidic sites are preferentially blocked by the soot; when the amount of carbon deposition is high (>2.6 wt.%), the soot started to block the micropores.
The TAP operation process is as follows: loading the catalyst into a reactor, wherein the upper part and the lower part of the reactor are filled with inert particles; a pulsed probe molecule (10)13Molecule/pulse) is injected into the reactor, and a vacuum (ultra-high vacuum system, pressure 1.333X 10) is drawn at the outlet-10kPa). Under high vacuum conditions, the molecules are transported following Knudsen diffusion, so if the residence time of the probe molecules in the reactor is delayed, it indicates that there is a kinetic interaction with the catalyst surface. The effluent from the reactor outlet was detected by a high sensitivity mass spectrometer.
So far, judging whether the newly developed MTO catalyst has good catalytic performance, the method mainly evaluates the reaction and checks the reaction activity and the selectivity of diolefin, and the process needs a long time.
Disclosure of Invention
The invention aims to provide a method for rapidly screening a catalyst with high selectivity of diolefin.
In order to achieve the purpose, main products of ethylene and propylene in the reaction of preparing olefin from methanol are selected as probe molecules to carry out TAP experiments. The specific screening method is as follows:
(1) 5-30mg of catalyst powder is filled in the reactor, and inert silicon carbide particles with the particle size of 210-250 mu m and the height of 0.5-5cm are filled up and down;
(2) vacuumizing the reactor, and then heating the reactor to 50-300 ℃ at the speed of 5-30 ℃/min;
(3) injecting mixed gas with the volume ratio of ethylene/inert gas ranging from (20/80) to (80/20) into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the mixed gas is connected with the outlet of the reactor, a quadrupole mass spectrum is connected with the mixed gas to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as an abscissa and the signal intensity as an ordinate, and the time from the peak appearance of the spectrogram to the peak appearance end is the retention time of the gas in a reactor bed layer;
(4) injecting mixed gas with the volume ratio of propylene to inert gas ranging from (20/80) to (80/20) into the reactor in a pulse mode, and detecting the residence time of the propylene gas;
(5) when the retention time sum tau of ethylene and propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the MTO reaction is poor; when tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the MTO reaction; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the MTO reaction.
The inert gas as described above is argon, helium, neon, krypton, or the like.
Compared with the prior art, the invention has the following advantages:
1. the method is simple to operate, the high-selectivity catalyst can be screened without MTO reaction evaluation on the catalyst, and the use of methanol is avoided;
2. the experimental time is short, and only a few seconds are needed for obtaining the required data;
3. the catalyst is less in use amount, and the optimization of the synthesis conditions in the early development process of the catalyst is greatly facilitated.
4. The accuracy rate is high when the average diolefin selectivity of the catalyst is judged.
Drawings
FIG. 1 is a schematic view of the reactor internal packing in TAP experiments.
FIG. 2 is a graph showing the residence time of ethylene in the A catalyst bed at 100 ℃.
FIG. 3 is a graph showing the residence time of propylene in the A catalyst bed at 100 ℃.
Detailed Description
Example 1
The catalyst was prepared according to the method of example 34 in U.S. Pat. No. 4,440,871, numbered A, and subjected to TAP experiments using ethylene/helium (at a volume ratio of 20/80) and propylene/krypton (at a volume ratio of 80/20) as probe molecules, respectively.
(1) Filling 8mg of catalyst powder into a reactor, and filling inert silicon carbide particles with the particle size of 210 mu m and the height of 1cm into the reactor from top to bottom;
(2) vacuumizing the reactor, and then heating the reactor to 100 ℃ at the speed of 10 ℃/min;
(3) injecting mixed gas ethylene/helium with the volume ratio of 20/80 into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the outlet of the reactor is connected with a quadrupole mass spectrum to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as the abscissa and the signal intensity as the ordinate, and the time from the peak appearance of the spectrogram to the peak appearance is the retention time of the gas in the bed layer of the reactor;
(4) injecting mixed gas of propylene/krypton gas with the volume ratio of 30/70 into the reactor in a pulse mode, detecting the residence time of the propylene gas, and repeating the steps (1) to (3);
(5) the residence time of ethylene and propylene in the catalyst bed layer A at 100 ℃ is respectively 0.90 s and 1.75s (shown in figures 2 and 3), and the sum of the residence time of the ethylene and the residence time of the propylene is 2.65 s;
(6) when the retention time sum tau of ethylene and propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the MTO reaction is poor; when tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the MTO reaction; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the MTO reaction.
(7) Therefore, it is known that the average diolefin selectivity of the A catalyst should be lower than 79%, and the catalytic performance of the A catalyst on MTO reaction is poor.
(8) The reaction temperature is 450 ℃, and the mass space velocity is 20h-1The MTO reaction evaluation of the catalyst A under the conditions of (1) was carried out to obtain an average diolefin selectivity of 78%, which was less than 79%, in agreement with the above conclusion.
Example 2
The catalyst was prepared according to the method of example 4 of patent application publication No. CN 104129800 a, No. B, and subjected to TAP experiments using ethylene/neon (volume ratio 40/60) and propylene/helium (volume ratio 70/30) as probe molecules, respectively.
(1) 15mg of catalyst powder is filled in a reactor, and inert silicon carbide particles with the height of 2cm and the particle size of 220 mu m are filled above and below the reactor;
(2) vacuumizing the reactor, and then heating the reactor to 110 ℃ at the speed of 15 ℃/min;
(3) injecting mixed gas ethylene/neon with the volume ratio of 40/60 into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the outlet of the reactor is connected with a quadrupole mass spectrum to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as the abscissa and the signal intensity as the ordinate, and the time from the peak appearance of the spectrogram to the peak appearance is the retention time of the gas in the bed layer of the reactor;
(4) injecting mixed gas propylene/helium with the volume ratio of 70/30 into the reactor in a pulse mode, detecting the residence time of the propylene gas, and repeating the steps (1) to (3);
(5) the detection shows that the residence time of ethylene and propylene in the catalyst bed layer B at 110 ℃ is 0.55 s and 1.50s respectively, and the sum of the residence time of the ethylene and the residence time of the propylene is 2.05 s;
(6) when the retention time sum tau of ethylene and propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the MTO reaction is poor; when tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the MTO reaction; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the MTO reaction.
(7) Accordingly, it was found that B had an average diolefin selectivity of 79 to 81% and exhibited good catalytic performance for MTO reaction.
(8) The reaction temperature is 500 ℃, and the mass space velocity is 100h-1The MTO reaction evaluation was carried out on B under the conditions of (1) to obtain an average diolefin selectivity of 80.6%, which was in agreement with the above-mentioned conclusion.
Example 3
The catalyst was prepared according to the method of example 4 of patent application publication No. CN 104326483 a, No. C, and subjected to TAP experiments using ethylene/argon (volume ratio 50/50) and propylene/neon (volume ratio 60/40) as probe molecules, respectively.
(1) Filling 20mg of catalyst powder into a reactor, and filling inert silicon carbide particles with the particle size of 230 mu m and the height of 3cm into the reactor from top to bottom;
(2) vacuumizing the reactor, and then heating the reactor to 125 ℃ at the speed of 20 ℃/min;
(3) injecting mixed gas ethylene/argon with the volume ratio of 50/50 into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the outlet of the reactor is connected with a quadrupole mass spectrum to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as the abscissa and the signal intensity as the ordinate, and the time from the peak appearance of the spectrogram to the peak appearance is the retention time of the gas in the bed layer of the reactor;
(4) injecting mixed gas propylene/neon with the volume ratio of 60/40 into the reactor in a pulse mode, detecting the residence time of the propylene gas, and repeating the steps (1) to (3);
(5) the detection shows that the residence time of the ethylene and the propylene in the C catalyst bed layer at 125 ℃ is 0.40 s and 1.40s respectively, and the sum of the residence time of the ethylene and the residence time of the propylene is 1.80 s;
(6) when the retention time sum tau of ethylene and propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the MTO reaction is poor; when tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the MTO reaction; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the MTO reaction.
(7) Accordingly, it was found that the average diolefin selectivity of the C catalyst was more than 81%, and the catalyst performance for the MTO reaction was excellent.
(8) The reaction temperature is 450 ℃, and the mass space velocity is 20h-1The evaluation of the MTO reaction of the C catalyst under the conditions of (1) was carried out to obtain an average diolefin selectivity of 81.1%, which was in agreement with the above-mentioned conclusion.
Example 4
A TAP experiment was performed on a catalyst prepared by the method of example 2 in patent publication No. CN 103896305 a, No. D, using ethylene/krypton (60/40 by volume) and propylene/argon (50/50 by volume) as probe molecules, respectively.
(1) Filling 25mg of catalyst powder into a reactor, and filling inert silicon carbide particles with the particle size of 240 mu m and the height of 4cm from top to bottom;
(2) vacuumizing the reactor, and then heating the reactor to 140 ℃ at the speed of 25 ℃/min;
(3) injecting mixed gas ethylene/krypton with the volume ratio of 60/40 into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the outlet of the reactor is connected with a quadrupole mass spectrometry to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as the abscissa and the signal intensity as the ordinate, and the time from the peak appearance of the spectrogram to the peak appearance is the retention time of the gas in the bed layer of the reactor;
(4) injecting mixed gas propylene/argon with the volume ratio of 50/50 into the reactor in a pulse mode, detecting the residence time of the propylene gas, and repeating the steps (1) to (3);
(5) the detection shows that the residence time of the ethylene and the propylene in the D catalyst bed layer at 140 ℃ is 0.36 s and 1.30s respectively, and the sum of the residence time of the ethylene and the residence time of the propylene is 1.66 s;
(6) when the retention time sum tau of ethylene and propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the MTO reaction is poor; when tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the MTO reaction; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the MTO reaction.
(7) Accordingly, it was found that the average diolefin selectivity of the D catalyst was more than 81%, and the catalyst performance for the MTO reaction was excellent.
(8) The reaction temperature is 450 ℃, and the mass space velocity is 20h-1The evaluation of the MTO reaction of the D catalyst under the conditions of (1) was carried out to obtain an average diolefin selectivity of 81.5%, which was in agreement with the above-mentioned conclusion.
Example 5
The catalyst was prepared according to the method of the comparative example in the patent publication No. CN 104326483 a, No. E, and subjected to TAP experiments using ethylene/argon (volume ratio 80/20) and propylene/krypton (volume ratio 20/80) as probe molecules, respectively.
(1) Filling 30mg of catalyst powder into a reactor, and filling inert silicon carbide particles with the particle size of 250 mu m and the height of 5cm into the reactor from top to bottom;
(2) vacuumizing the reactor, and then heating the reactor to 150 ℃ at the speed of 30 ℃/min;
(3) injecting mixed gas ethylene/argon with the volume ratio of 80/20 into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the outlet of the reactor is connected with a quadrupole mass spectrum to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as the abscissa and the signal intensity as the ordinate, and the time from the peak appearance of the spectrogram to the peak appearance is the retention time of the gas in the bed layer of the reactor;
(4) injecting mixed gas of propylene/krypton gas with the volume ratio of 20/80 into the reactor in a pulse mode, detecting the residence time of the propylene gas, and repeating the steps (1) to (3);
(5) the detection shows that the residence time of ethylene and propylene in the E catalyst bed layer at 150 ℃ is 0.30 s and 1.25s respectively, and the sum of the residence time of the ethylene and the residence time of the propylene is 1.55 s;
(6) when the retention time sum tau of ethylene and propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the MTO reaction is poor; when tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the MTO reaction; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the MTO reaction.
(7) Accordingly, it was found that the average diolefin selectivity of the E catalyst was more than 81%, and the catalyst performance for MTO reaction was excellent.
(8) The reaction temperature is 450 ℃, and the mass space velocity is 20h-1The evaluation of the MTO reaction of the E catalyst under the conditions of (1) was carried out to obtain an average diolefin selectivity of 81.9%, which was in agreement with the above-mentioned conclusion.
When the temperature of the catalyst bed is between 100 ℃ and 150 ℃, the average diolefin selectivity of the reaction for catalyzing methanol to olefin by each catalyst has certain correlation with the residence time of ethylene or propylene. When the temperature is too high, the interaction force of ethylene or propylene and the surface of the catalyst is weak, and the retention time is short; when the temperature is too low, the interaction force of ethylene or propylene with the catalyst surface is strong and the residence time is long.
The average diolefin selectivity and the residence time of ethylene and propylene of the reaction for catalyzing the methanol to olefin reaction by each catalyst are listed in the first table, and the residence time of propylene at the same temperature is higher than that of ethylene, which shows that the interaction between the propylene and the catalyst pore channels is higher than that of the ethylene.
It is understood from the table I that the average diolefin selectivity decreases with increasing ethylene or propylene residence time.
The above phenomenon is because the ethylene and the propylene have interaction with the catalyst when contacting, the larger the interaction is, the longer the retention time is, the more difficult the ethylene and the propylene escape from the catalyst pore channel; when methanol is used for preparing olefin, ethylene and propylene are generated in microporous pore channels of the catalyst, and if the ethylene and the propylene are difficult to quickly escape from the pore channels, secondary reaction is easy to occur in the pore channels, so that the selectivity of diolefin is reduced. The retention time of propylene in the catalyst bed is longer than that of ethylene, which means that propylene is more difficult to escape, and thus the selectivity of propylene is lower than that of ethylene, so that the average ratio of ethylene to propylene is more than 1 for most of the catalysts (outside A).
When TAP technology is used for testing a certain catalyst, if the sum of the retention time of ethylene and propylene (represented by tau, and the unit of s) is more than 2.40s, the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst is poor; if tau is between 1.82 and 2.40s, the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalytic performance is good; if tau is less than 1.82s, the average diolefin selectivity of the catalyst is more than 81 percent, and the catalyst performance is excellent. Therefore, the method can quickly and effectively screen the methanol-to-olefin catalyst with high selectivity of diolefin.
TABLE average diolefin Selectivity and Retention time for the MTO reaction on different catalysts
Claims (2)
1. A method for rapidly screening a high-selectivity methanol-to-olefin catalyst is characterized by comprising the following steps:
(1) 5-30mg of catalyst powder is filled in the reactor, and inert silicon carbide particles with the particle size of 210-250 mu m and the height of 0.5-5cm are filled up and down;
(2) vacuumizing the reactor, and then heating the reactor to 50-300 ℃ at the speed of 5-30 ℃/min;
(3) injecting mixed gas with the volume ratio of ethylene/inert gas of 20/80-80/20 into a reactor in a pulse mode, wherein the pulse time is 360 mu s, the outlet of the reactor is connected with a quadrupole mass spectrum to detect the ethylene gas escaping from the reactor, a spectrogram is formed by taking the time as an abscissa and the signal intensity as an ordinate, and the time from the peak appearance of the spectrogram to the peak appearance is the retention time of the gas in a reactor bed layer;
(4) injecting mixed gas with the volume ratio of propylene to inert gas being in the range of 20/80-80/20 into the reactor in a pulse mode, and detecting the residence time of the propylene gas;
(5) when the sum tau of the retention time of the ethylene and the propylene is more than 2.40s, judging that the average diolefin selectivity of the catalyst is less than 79 percent, and the catalytic performance of the catalyst on the reaction of preparing olefin from methanol is poor; when the tau is between 1.82 and 2.40s, judging that the average diolefin selectivity of the catalyst is between 79 and 81 percent, and the catalyst has good catalytic performance on the reaction of preparing olefin from methanol; when tau is less than 1.82s, the average diolefin selectivity of the catalyst is judged to be more than 81%, and the catalyst has excellent catalytic performance on the reaction of preparing olefin from methanol.
2. The method of claim 1, wherein the inert gas is argon, helium, neon, or krypton.
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Citations (2)
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|---|---|---|---|---|
| US4626412A (en) * | 1984-12-14 | 1986-12-02 | Monsanto Company | Method and apparatus for carrying out catalyzed chemical reactions and for studying catalysts |
| US6087180A (en) * | 1993-04-30 | 2000-07-11 | Gleaves; John T. | Method for study and analysis of products of catalytic reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4626412A (en) * | 1984-12-14 | 1986-12-02 | Monsanto Company | Method and apparatus for carrying out catalyzed chemical reactions and for studying catalysts |
| US6087180A (en) * | 1993-04-30 | 2000-07-11 | Gleaves; John T. | Method for study and analysis of products of catalytic reaction |
Non-Patent Citations (4)
| Title |
|---|
| TAP reactor study of the partial oxidation of methanol to formaldehyde using an industrial Fe-Cr-Mo oxide catalyst;David S. Lafyatis et al.;《Applied Catalysis A: General》;19941231;第120卷(第1期);第85-103页 * |
| Temporal analysis of products: basic principles, applications, and theory;G.S. Yablonsky et. al.;《Journal of Catalysis》;20030630;第216卷(第1-2期);第120-134页 * |
| The conversion of methanol to ole"ns: a transient kinetic study;Olivier Dewaele et al.;《Chemical Engineering Science》;19991031;第54卷(第20期);第4385-4395页 * |
| 固体催化剂的研究方法 第十二章 产物瞬时分析(TAP)技术;王德峥 等;《石油化工》;20011130;第30卷(第11期);第884-892页 * |
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