CN107185542B - Supported Fe-Zn/CNTs catalyst and preparation method thereof - Google Patents
Supported Fe-Zn/CNTs catalyst and preparation method thereof Download PDFInfo
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- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
The invention discloses a supported Fe-Zn/CNTs catalyst and a preparation method thereof. The catalyst comprises the following components: the active metal Fe, Zn and the carbon nano tube carrier are 10-25% of total mass fraction of Fe and Zn based on the weight of the carbon nano tube, wherein the molar ratio of Fe to Zn is 0.5: 1-1.5: 1. The catalyst is prepared by adopting the following method: treating the carbon nano tube by adopting inorganic acid under the ultrasonic condition, and then washing and drying; preparing a mixed solution containing Fe, Zn and urea; and introducing the prepared mixed solution into a treated carbon nano tube carrier, pressurizing and dipping the carbon nano tube carrier, heating the carbon nano tube carrier, and then drying and roasting the carbon nano tube carrier to obtain the catalyst. The catalyst of the invention is suitable for the reaction of directly preparing olefin from synthesis gas, and can greatly reduce CH4Selectivity of, increase C2‑C4The selectivity of olefin and the activity of the catalyst are better.
Description
Technical Field
The invention relates to a composite crystal metal supported catalyst and a preparation method thereof, in particular to a Fe-Zn/CNTs catalyst and a preparation method thereof.
Background
The low-carbon olefins such as ethylene, propylene, 1-butene, etc. are important petrochemical products and chemical raw materials, the yield of the low-carbon olefins reflects the level of the national petrochemical industry, the demand of the low-carbon olefins is continuously increased along with the steady increase of the Chinese economy, and the contradiction between supply and demand is still sharp. The technology for directly preparing the low-carbon olefin from the synthesis gas prepared from coal, biomass, industrial tail gas and natural gas through the Fischer-Tropsch synthesis process by combining the resource characteristics of oil shortage, less gas and more coal in China shows good application prospect. The research on the traditional Fe-based and Co-based catalysts is relatively mature, and the application research of bimetallic catalysts in F-T synthesis is gradually a hotspot. Due to the addition of the second metal component, interaction between the two metals occurs, which can change the catalytic performance of a single metal. Meanwhile, the carbon nano tube becomes a popular choice for the catalyst carrier due to good thermal conductivity, strong adsorption performance, unique pore channel structure and generated 'confinement effect'.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a Fe-Zn/CNTs catalyst and a preparation method thereof. The catalyst of the invention is suitable for the reaction of directly preparing olefin from synthesis gas, and can greatly reduce CH4Selectivity of, increase C2~C4The selectivity of olefin and the activity of the catalyst are better.
The invention provides a load type Fe-Zn/CNTs catalyst, which comprises the following components: the active metal is Fe and Zn, the carrier is a carbon nano tube, and the total mass fraction of Fe and Zn is 10-25% based on the weight of the carbon nano tube; wherein the molar ratio of Fe to Zn is 0.5: 1-1.5: 1.
In the supported Fe-Zn/CNTs catalyst, the mass of Fe and Zn distributed in the CNTs accounts for 70-87%, preferably 75-85% of the total mass of the Fe and the Zn.
In the supported Fe-Zn/CNTs catalyst, CNTs represent carbon nanotubes, the carbon nanotubes are preferably MWCNTs (represent multi-walled carbon nanotubes), and the outer diameter of the carbon nanotubes is 10-30 nm.
The preparation method of the supported Fe-Zn/CNTs catalyst comprises the following steps:
(1) treating the carbon nano tube by adopting inorganic acid under the ultrasonic condition, and then washing and drying;
(2) preparing a mixed solution containing Fe, Zn and urea;
(3) and (3) introducing the mixed solution obtained in the step (2) into the carbon nano tube carrier obtained in the step (1), pressurizing, dipping, heating to 80-100 ℃, keeping for 2-4 hours, drying and roasting to obtain the catalyst.
The carbon nano tube in the step (1) is preferably treated by inorganic acid and is modified by heating and refluxing. The inorganic acid is H2SO4And HNO3In which H is2SO4And HNO3The volume ratio of (A) to (B) is 1.5:1 to 2.5: 1. In the mixed acid solution, H2SO4The concentration of (A) is 15.0-18.4 mol/L, HNO3The concentration of (A) is 10.0-14.5 mol/L, and the volume ratio of the mixed acid to the carbon nano tube is 2-10, preferably 4-8.
The ultrasonic conditions in the step (1) are as follows: the ultrasonic frequency is 30-80 KHz, and the time duration is 2-6 h.
The heating reflux conditions in the step (1) are as follows: the reflux temperature is 120-150 ℃, and the reflux time is 8-16 h.
The washing in the step (1) is to wash the mixture to be neutral by using deionized water, and preferably vacuum filtration is carried out firstly.
The drying conditions in step (1) are as follows: drying for 4-12 h at 60-120 ℃.
In the step (2), the mole number of the urea in the mixed solution containing Fe, Zn and urea is 1.5-8.0 times of the total mole number of Fe and Zn.
In the step (3), the process of introducing the mixed solution obtained in the step (2) into the carbon nanotube carrier obtained in the step (1) is as follows: adding the mixed solution prepared in the step (2) into a storage solution tank, simultaneously placing a carbon nano tube carrier into a vacuum pressure impregnation reactor, vacuumizing the impregnation reactor by 30-50 Pa, opening a liquid suction pipe valve to suck the solution into the impregnation reactor, and closing the valve. Adding the mixed solution obtained in the step (2) into an impregnation reactor in an amount calculated by equal volume impregnation.
The pressure impregnation process in the step (3) is as follows: and applying pressure to the impregnation reactor to a required value of 10-12 MPa, and then keeping the pressure for 2-8 hours.
The drying and roasting conditions in the step (3) are as follows: drying at 40-80 ℃ for 8-12 h, and then adding N2Roasting for 2-6 h at 300-400 ℃ under protection.
The catalyst of the invention is suitable for the reaction of directly preparing olefin by synthesis gas, and the reaction conditions are as follows: the reaction temperature is 250-310 ℃, the pressure is 1.5-2.5 MPa, and the molar ratio of the raw material synthesis gas is H2：CO：CO2=2 to 4: (6-8): 1, the volume airspeed of the raw material is 1500-3000 h-1。
Compared with the prior art, the invention has the following advantages:
1. compared with a single non-noble metal catalyst, the supported Fe-Zn/CNTs catalyst has higher catalytic activity and low-carbon olefin selectivity due to the strong synergistic effect between bimetallic Fe and Zn nanoparticles, particularly the ratio of metal nanoparticles distributed inside and outside the CNTs is controlled, so that the supported Fe-Zn/CNTs catalyst shows higher catalytic activity and low-carbon olefin selectivity.
2. The preparation method of the supported Fe-Zn/CNTs catalyst adopts a method of vacuum impregnation liquid introduction and pressure impregnation, so that a proper amount of metal enters the interior of the carbon nano-tubes, and the proportion of the metal nano-particles distributed inside and outside the CNTs is controlled, thereby improving the conversion rate of CO and the selectivity of low-carbon olefin in the product.
3. The catalyst of the invention is suitable for the reaction of directly preparing olefin from synthesis gas, and can greatly reduce CH4Selectivity of, increase C2-C4Olefin selectivity, catalyst activity.
Detailed Description
The following non-limiting examples enable those skilled in the art to understand the technical solutions of the present invention in more detail, but do not limit the invention in any way.
Example 1
(1) Adding 10g of MWCNTs with the pipe diameter of 10-20 nm into concentrated H2SO4And concentrated HNO3And ultrasonic treatment is adopted. Wherein the volume ratio of the mixed acid to the MWCNTs is 5, wherein H2SO4And HNO3In a volume ratio of 2:1, H2SO4Has a concentration of 18.4mol/L, HNO3The concentration of (A) is 14.5mol/L, and the ultrasonic condition is as follows: and (5) carrying out ultrasonic treatment for 4h at 60 KHz. Then using a heating stirring reflux device to carry out azeotropic reflux at 140 DEG C1And (3) carrying out vacuum filtration for 2h, washing with deionized water to be neutral, drying at 60 ℃ for 10h, and grinding into powder for later use.
(2) Firstly, Fe (NO) with a molar ratio of 1:1 is weighed3)3•9H2O and Zn (NO)3)2•6H211.60g of O and 5g of urea are dissolved in a proper amount of deionized water. The prepared mixed salt solution is obtained, wherein the amount of the deionized water is calculated according to the equal volume of the impregnation.
(3) And (3) adding the prepared solution into a storage solution tank, and simultaneously putting the multi-walled carbon nano tube obtained in the step (1) into a vacuum pressure impregnation reactor. And then, vacuumizing the impregnation reactor to the required vacuum degree of 50Pa, opening a liquid suction pipe valve to suck the solution into the impregnation reactor, then closing the valve, ventilating and pressurizing the impregnation reactor through a gas path until the pressure reaches the required value of 11MPa and becomes stable, and then beginning pressure-maintaining impregnation for 8 h. The impregnation reactor was then warmed to 90 ℃ for 2 h.
The impregnated catalyst was removed, dried at 60 ℃ for 10h and then placed in a tube furnace at a flow rate of 60mL/min N2Roasting at 350 ℃ for 4h under protection to obtain the Fe-Zn/MWCNTs catalyst Cat1, wherein Fe and Zn account for 20% of the weight of the multi-walled carbon nano-tube, and Fe and Zn distributed in the CNTs account for 85% of the total mass of Fe and Zn in the catalyst.
Example 2
The procedure was carried out in approximately the same way as in example 1, wherein Fe and Zn account for 20% by weight of the multi-walled carbon nanotubes. With the difference that Fe (NO) in step 23)3·9H2O and Zn (NO)3)2·6H2The molar ratio of O was 0.5:1 to obtain catalyst Cat 2. In Cat2, Fe and Zn distributed in CNTs account for 82% of the total mass of Fe and Zn in the catalyst.
Example 3
The procedure was carried out in approximately the same way as in example 1, wherein Fe and Zn account for 20% by weight of the multi-walled carbon nanotubes. With the difference that Fe (NO) in step 23)3·9H2O and Zn (NO)3)2·6H2The molar ratio of O was 1.5:1, giving catalyst Cat 3. In Cat3And Fe and Zn distributed in the CNTs account for 80 percent of the total mass of Fe and Zn in the catalyst.
Example 4
The specific implementation procedure was substantially the same as example 1, except that in step 2, Fe and Zn accounted for 10% of the weight of the multiwall carbon nanotubes, and the molar ratio of urea to the total of Fe and Zn was 2:1, resulting in catalyst Cat 4. In Cat4, Fe and Zn distributed in CNTs account for 75% of the total mass of Fe and Zn in the catalyst.
Example 5
The specific implementation process is substantially the same as that of the embodiment 1, and the difference is that in the step 2, a multi-walled carbon nanotube with the tube diameter of 20-30 nm is used as a carrier; and (3) obtaining a catalyst Cat5 under the vacuum degree of 40Pa and the pressurizing condition of 12 MPa. In Cat5, Fe and Zn distributed in CNTs account for 85% of the total mass of Fe and Zn in the catalyst.
Example 6
The procedure was carried out in substantially the same manner as in example 1, except that the amount of urea added in step 2 was 8 g. Catalyst Cat6 was obtained. In Cat6, Fe and Zn distributed in CNTs account for 80% of the total mass of Fe and Zn in the catalyst.
Comparative example 1
The specific procedure was carried out in substantially the same manner as in example 1, except that Fe (NO) was used3)3·9H2O and Zn (NO)3)2·6H2The molar ratio of O is 1:0, namely the supported pure Fe catalyst is obtained, and the DCat1 is obtained without supporting Zn.
Comparative example 2
The specific implementation process steps (1) and (2) are the same as example 1, except that step (3): and (3) adding the solution prepared in the step (2) and the multi-walled carbon nano-tube obtained in the step (1) into a common impregnation reactor, and impregnating for 8 hours by adopting an isometric impregnation method. The impregnation reactor was then warmed to 90 ℃ for 2 h.
Example 7
The evaluation of the catalyst was mainly carried out on a micro-evaluation device. The evaluation flow mainly comprises the following steps: catalyst filling, reaction system tightness detection, catalyst reduction, hydrogenation reaction and online chromatographic analysis.
Weighing Fe-Zn/MWCNTs catalyst Cat 11 g, filling into a reaction tube, and using the volume flow ratio of 60mL/min H under the pressure of 0.2MPa2And (4) carrying out reduction. And (4) programming the temperature to 350 ℃, reducing for 4 hours at constant temperature, then naturally cooling, and finishing the reduction process. CO in preparation of low-carbon olefin from synthetic gas2Is also one of the by-products, and according to the principle of Lexhlet, CO is added into the raw material gas2Will inhibit the WGS reaction from occurring; at the same time, the H in the catalyst is ensured2The condition of/CO =2, therefore the raw material synthesis gas ratio is H2/CO/CO2=3:8: 1. The reaction conditions were as follows: the reaction pressure is 2MPa, and the gas space velocity is 2500h-1The reaction temperature is 280 ℃; after the reaction, the product was introduced into a gas chromatograph for on-line analysis, and the reaction results are shown in table 1.
Examples 8 to 12
The procedure of example 7 was followed except that Cat2-Cat6 prepared in examples 2-6 were used in place of Cat1, respectively, and the results after the reaction are shown in Table 1.
Comparative examples 3 and 4
The procedure of example 7 was followed except that the catalysts DCat1 and DCat2 prepared in comparative examples 1-2 were used in place of Cat1, respectively, and the results after the reaction are shown in Table 1.
TABLE 1 evaluation results of catalysts of examples and comparative examples
| Examples | Catalyst and process for preparing same | Fe/Zn | XCO | SCO2 | SCH4 |
| Example 7 | Cat1 | 1：1 | 92.09 | 15.79 | 15.23 |
| Example 8 | Cat2 | 0.5：1 | 90.04 | 16.56 | 16.46 |
| Example 9 | Cat3 | 1.5：1 | 91.46 | 16.13 | 18.22 |
| Example 10 | Cat4 | 1：1 | 90.07 | 15.23 | 16.23 |
| Example 11 | Cat5 | 1：1 | 91.55 | 15.43 | 16.30 |
| Example 12 | Cat6 | 1：1 | 91.83 | 15.54 | 15.76 |
| Comparative example 3 | DCat1 | 1：0 | 85.76 | 30.51 | 23.31 |
| Comparative example 4 | DCat2 | 1：1 | 86.37 | 25.26 | 22.41 |
TABLE 1 continuation
| Examples | Catalyst and process for preparing same | Fe/Zn | SC2 0 -C4 0 | SC2 = -C4 = | SC5 + |
| Example 7 | Cat1 | 1：1 | 7.72 | 54.32 | 12.36 |
| Example 8 | Cat2 | 0.5：1 | 8.04 | 50.94 | 17.56 |
| Example 9 | Cat3 | 1.5：1 | 8.67 | 53.10 | 20.01 |
| Example 10 | Cat4 | 1：1 | 7.92 | 52.34 | 23.51 |
| Example 11 | Cat5 | 1：1 | 9.20 | 52.26 | 22.24 |
| Example 12 | Cat6 | 1：1 | 8.45 | 54.12 | 21.67 |
| Comparative example 3 | DCat1 | 1：0 | 23.40 | 34.52 | 18.77 |
| Comparative example 4 | DCat2 | 1：1 | 7.47 | 52.55 | 17.57 |
Note that in table 1, the following examples are given,
XCO-CO conversion,% (mole fraction);
SCO2---CO2selectivity,% (mole fraction);
SCH4--- CH4yield,% (mole fraction);
SC2 0 -C4 0--- C2~C4alkane selectivity,% (mole fraction);
SC2 = -C4 =--- C2~C4olefin selectivity,% (mole fraction);
SC5 +--- C5+selectivity,% (mole fraction).
As can be seen from Table 1, the catalyst of the present invention can greatly reduce CH when used in the reaction of directly preparing olefin from synthesis gas4Selectivity of, increase C2-C4The selectivity of olefin and the activity of the catalyst are better.
Claims (11)
1. A supported Fe-Zn/CNTs catalyst comprises the following components: the composite material comprises active metal and a carrier, wherein the active metal is Fe and Zn, the carrier is a carbon nano tube, and the total mass fraction of Fe and Zn is 10-25% by taking the weight of the carbon nano tube as a reference; wherein the molar ratio of Fe to Zn is 0.5: 1-1.5: 1; wherein, the mass of Fe and Zn distributed in the CNTs accounts for 70-87% of the total mass of Fe and Zn in the catalyst.
2. The catalyst of claim 1, wherein: the mass of Fe and Zn distributed in the CNTs accounts for 75-85% of the total mass of Fe and Zn in the catalyst.
3. The catalyst of claim 1, wherein: the carbon nano tube is a multi-wall carbon nano tube; the outer diameter of the carbon nano tube is 10-30 nm.
4. A process for preparing the catalyst of any one of claims 1 to 3, comprising:
(1) treating the carbon nano tube by adopting inorganic acid under the ultrasonic condition, and then washing and drying;
(2) preparing a mixed solution containing Fe, Zn and urea;
(3) and (3) introducing the mixed solution obtained in the step (2) into the carbon nano tube carrier obtained in the step (1) under a vacuum condition, pressurizing and dipping, heating to 80-100 ℃, keeping for 2-4 hours, drying and roasting to obtain the catalyst.
5. The method of claim 4, wherein: in the step (1), the carbon nano tube is treated by inorganic acid and is modified by heating and refluxing; the ultrasonic conditions were as follows: the ultrasonic frequency is 30-80 KHz, and the time duration is 2-6 h; the heating reflux conditions are as follows: the reflux temperature is 120-150 ℃, and the reflux time is 8-16 h; the washing is to wash the mixture to be neutral by using deionized water; the drying conditions were as follows: drying for 4-12 h at 60-120 ℃.
6. The method of claim 5, wherein: the inorganic acid is H2SO4And HNO3In which H is2SO4And HNO3In the mixed acid solution, H is added in the mixed acid solution in a volume ratio of 1.5: 1-2.5: 12SO4The concentration of (A) is 15.0-18.4 mol/L, HNO3The concentration of (A) is 10.0-14.5 mol/L, and the volume ratio of the mixed acid to the carbon nano tube is 2-10.
7. The method of claim 6, wherein: the volume ratio of the mixed acid to the carbon nano tube is 4-8.
8. The method of claim 4, wherein: in the mixed solution obtained in the step (2), the mole number of urea is 1.5-8.0 times of the total mole number of Fe and Zn; in the step (3), the process of introducing the mixed solution obtained in the step (2) into the carbon nanotube carrier obtained in the step (1) is as follows: adding the mixed solution prepared in the step (2) into a storage solution tank, simultaneously placing a carbon nano tube carrier into a vacuum pressure impregnation reactor, vacuumizing the impregnation reactor by 30-50 Pa, opening a liquid suction pipe valve to suck the solution into the impregnation reactor, and closing the valve; adding the mixed solution obtained in the step (2) into an impregnation reactor in an amount calculated by equal volume impregnation.
9. The method of claim 4, wherein: the pressure impregnation process in the step (3) is as follows: and applying pressure to 10-12 MPa in the impregnation reactor, and then keeping the pressure for 2-8 h.
10. The method of claim 4, wherein: the drying and roasting conditions in the step (3) are as follows: drying at 40-80 ℃ for 8-12 h, and then adding N2Roasting for 2-6 h at 300-400 ℃ under protection.
11. A method for directly preparing olefin from synthesis gas is characterized by comprising the following steps: the catalyst of any one of claims 1 to 3, wherein the reaction conditions are as follows: the reaction temperature is 250-310 ℃, the pressure is 1.5-2.5 Mpa, and the molar ratio of the raw material synthesis gas is H2：CO：CO2(2-4): (6-8): 1, the volume airspeed of the raw material is 1500-3000 h-1。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698764A (en) * | 2012-06-07 | 2012-10-03 | 北京石油化工学院 | Catalyst used in preparation of low-carbon olefins by using synthesis gas and preparation method and application of catalyst |
| CN106311237A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Iron carbon-based composite porous material catalyst and preparation method and application thereof |
| CN106540689A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of CNT carried palladium catalyst and its preparation method and application |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698764A (en) * | 2012-06-07 | 2012-10-03 | 北京石油化工学院 | Catalyst used in preparation of low-carbon olefins by using synthesis gas and preparation method and application of catalyst |
| CN106311237A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Iron carbon-based composite porous material catalyst and preparation method and application thereof |
| CN106540689A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of CNT carried palladium catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "Iron catalyst encapsulated in carbon nanotubes for CO hydrogenation to light olefins";Xiaoqi Chen et al;《Chinese Journal of Catalysis》;20150920;第36卷(第9期);第1631-1637页 * |
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