CN114870886A - Preparation method and application of catalyst for directly preparing gasoline by carbon dioxide hydrogenation - Google Patents

Preparation method and application of catalyst for directly preparing gasoline by carbon dioxide hydrogenation Download PDF

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CN114870886A
CN114870886A CN202210637755.7A CN202210637755A CN114870886A CN 114870886 A CN114870886 A CN 114870886A CN 202210637755 A CN202210637755 A CN 202210637755A CN 114870886 A CN114870886 A CN 114870886A
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catalyst
carbon dioxide
zsm
reaction
molecular sieve
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王承东
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a preparation method and application of a catalyst for directly preparing gasoline by carbon dioxide hydrogenation. The preparation method comprises the following steps: mixing Na element-containing metal salt and Fe element-containing metal salt with a solution of a precipitator, and reacting to obtain a precipitate; aging, washing, drying and roasting the precipitate to obtain Na and Fe metal oxides Na-Fe 3 O 4 (ii) a Preparing a dipping solution for the metal oxide; mixing the impregnation liquid with a ZSM-5 molecular sieve, and processing to obtain the multifunctional composite catalyst Na-Fe 3 O 4 ZSM-5. The application is as follows: activating a catalyst in an inert gas Na atmosphere, introducing a mixed gas of carbon dioxide and hydrogen for reaction, and finally cooling and collecting a liquid-phase product. The catalyst has excellent catalytic performance, CO 2 High conversion rate, C in gasoline hydrocarbon product as target product 5 The highest rate of the reaction is more than 80.2 percent, the reaction is stable, the cost is low, and the preparation process is simpleAnd (3) the method is simple and easy for industrial production.

Description

Preparation method and application of catalyst for directly preparing gasoline by carbon dioxide hydrogenation
Technical Field
The invention relates to the technical field of energy and the fields of greenhouse gas emission and carbon dioxide resource utilization, in particular to a preparation method and application of a catalyst for directly preparing gasoline by carbon dioxide hydrogenation.
Background
Carbon dioxide is used as a carbon resource which exists in a large amount in the nature, hydrogen produced by electrolyzing water by means of solar energy is converted into liquid fuel with high added value, so that the problem of environmental problem caused by increase of carbon dioxide in the atmosphere and excessive dependence on fossil fuel can be solved.
Hydrocarbon compounds such as gasoline are important transportation fuels and are widely applied worldwide, so that the hydrogenation of carbon dioxide to prepare gasoline is considered to be a potential target product. Since carbon dioxide is inert and difficult to convert compounds containing more than two carbon atoms, an effective catalyst needs to be developed to solve the problem of application of hydrogenation of carbon dioxide to gasoline.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and an application of a catalyst for directly preparing gasoline by carbon dioxide hydrogenation.
The technical scheme of the invention is as follows:
a catalyst for preparing gasoline directly by hydrogenating carbon dioxide is composed of metal oxide and ZSM-5 molecular sieve.
The metal oxide accounts for 20-80% of the mass of the catalyst, and the metal oxide comprises Na-Fe 3 O 4 (ii) a The ZSM-5 molecular sieve accounts for 20-80% of the weight of the catalyst, and the ZSM-5 molecular sieve is selected from Al 2 O 3 。
A preparation method of a catalyst for directly preparing gasoline by carbon dioxide hydrogenation comprises the following steps:
(1) mixing metal salt containing Na element and metal salt solution containing Fe element with precipitant solution, and reacting to obtain precipitate;
(2) aging, washing, drying and roasting the precipitate obtained in the step (1) to obtain Na and Fe metal oxide Na-Fe 3 O 4 ；
(3) Dissolving the obtained Na and Fe element metal oxides in water by adopting an isometric impregnation method to prepare an impregnation solution;
(4) mixing and processing the impregnation liquid of Na and Fe element metal oxides and the ZSM-5 molecular sieve to obtain the multifunctional composite catalyst: Na-Fe 3 O 4 /ZSM-5。
The application of the catalyst for directly preparing gasoline by carbon dioxide hydrogenation is characterized in that the catalytic reaction for preparing gasoline by carbon dioxide hydrogenation is carried out in a fixed bed catalytic reaction tower, the catalyst is activated in the atmosphere of inert gas Na before the reaction, then mixed gas of carbon dioxide and hydrogen is introduced for reaction, and finally the reaction product is cooled to room temperature to collect a liquid phase product.
The invention has the beneficial effects that:
the catalyst of the invention has excellent catalytic performance, CO 2 High conversion rate, high selectivity of gasoline hydrocarbon compound as target product, and C in hydrocarbon product 5 The highest rate can be more than 80.2 percent. Byproduct AThe alkane and CO have low selectivity, stable reaction, low cost, simple preparation process and easy industrial production.
Detailed Description
The invention discloses a preparation method and application of a catalyst for directly preparing gasoline by carbon dioxide hydrogenation. The catalyst comprises a metal oxide and a ZSM-5 molecular sieve. The metal oxide accounts for 20-80% of the mass of the catalyst, and the metal oxide comprises Na-Fe 3 O 4 (ii) a The ZSM-5 molecular sieve accounts for 20-80% of the weight of the catalyst, and the ZSM-5 molecular sieve is selected from Al 2 O 3 。
The preparation method of the composite catalyst comprises the following steps:
(1) and mixing the metal salt containing the Na element and the metal salt solution containing the Fe element with a precipitator solution, and reacting to obtain a precipitate. The Na element-containing metal salt is preferably sodium nitrite (NaNO) 2 ) The Fe-containing metal salt is preferably ferrous oxide (FeO). The precipitant is general inorganic precipitant, such as polyaluminum ferric chloride, polyferric sulfate, etc. The concentrations of the Na element-containing metal salt solution and the Fe element-containing metal salt solution are respectively 0.5-1mol/L, and the concentration of the precipitator is 0.1-1 mol/L. The volume ratio of the three solutions is as follows: 20% -30% -50%.
(2) Aging, washing, drying and roasting the precipitate obtained in the step (1) to obtain Na and Fe metal oxides (namely Na-Fe) 3 O 4 )。
(3) And dissolving the obtained Na and Fe element metal oxides in water by adopting an isometric impregnation method to prepare an impregnation solution.
(4) Mixing and processing the impregnation liquid of Na and Fe element metal oxides and the ZSM-5 molecular sieve to obtain the multifunctional composite catalyst: Na-Fe 3 O 4 /ZSM-5。
Wherein:
in the step (1), the reaction temperature is 10-40 ℃.
In the step (2), the aging temperature is 40-100 ℃, and the aging time is 1-10H; the drying temperature is 60-100 ℃, and the drying time is 6-24H; the roasting temperature is 250-500 ℃, and the roasting time is 2-12H.
Step (4)) In the mixing, the ZSM-5 molecular sieve is immersed in the impregnating solution, the Na and Fe element metal oxide components in the impregnating solution are adhered on the molecular sieve body, namely in the pore channels, and the standing time is 16-24H. The processing comprises the following steps: will be attached with Na-Fe 3 O 4 Roasting the ZSM-5 molecular sieve of the metal oxide (the roasting temperature is 250-500 ℃, and the roasting time is 8-12H); and then mechanically ball-milling, pressing and sieving to obtain particles of 20-80 meshes, filling the particles into a container, and vibrating to realize uniform mixing to obtain the Na-Fe3O4/ZSM-5 multifunctional composite catalyst.
The application of the catalyst of the invention is as follows:
the catalytic reaction for preparing gasoline by carbon dioxide hydrogenation is carried out in a fixed bed catalytic reaction tower.
Before the reaction, the catalyst is activated in the atmosphere of inert gas Na at the activation temperature of 400 ℃ and 500 ℃ for 5-12 hours. Then introducing mixed gas of carbon dioxide and hydrogen to react, wherein the molar ratio of the carbon dioxide to the hydrogen is 4: 1. The reaction conditions are as follows: the reaction temperature is 350-500 ℃, the reaction pressure is 1-7mpa, the space velocity is 500-50000ml/h, and finally the liquid phase product is collected after cooling to the room temperature.
The hydrocarbon gas chromatography analysis results of the product evaluations are given in the following table:
conversion rate Selectivity is CH4 C2-C4 C5
22.4％ 34％ 2.1 29.4 68.5
As can be seen from the table, when the catalyst is used in the reaction of preparing gasoline by carbon dioxide hydrogenation, the target selectivity of the product is improved and is high.
Example (b): the catalyst is catalyzed at 1-5mpa, the reaction temperature is 350- 2 /H 2 CO at a molar ratio of 4: 1 2 High conversion rate, low deactivation rate and strong stability.
The above description is only a preferred embodiment of the present invention, and other embodiments are within the scope of the present invention without any inventive step for those skilled in the art.

Claims (10)

1. A catalyst for directly preparing gasoline by carbon dioxide hydrogenation is characterized in that: the catalyst comprises a metal oxide and a ZSM-5 molecular sieve.
2. The catalyst of claim 1, wherein: the metal oxide accounts for 20-80% of the mass of the catalyst, and the metal oxide comprises Na-Fe 3 O 4 (ii) a The ZSM-5 molecular sieve accounts for 20-80% of the weight of the catalyst, and the ZSM-5 molecular sieve is selected from Al 2 O 3 。
3. A preparation method of a catalyst for directly preparing gasoline by carbon dioxide hydrogenation comprises the following steps:
(1) mixing metal salt containing Na element and metal salt solution containing Fe element with precipitant solution, and reacting to obtain precipitate;
(2) aging, washing, drying and roasting the precipitate obtained in the step (1) to obtain Na and Fe metal oxide Na-Fe 3 O 4 ；
(3) Dissolving the obtained Na and Fe element metal oxides in water by adopting an isometric impregnation method to prepare an impregnation solution;
(4) mixing and processing the impregnation liquid of Na and Fe element metal oxides and the ZSM-5 molecular sieve to obtain the multifunctional composite catalyst: Na-Fe 3 O 4 /ZSM-5。
4. The production method according to claim 3, characterized in that: in the step (1), the Na element-containing metal salt is sodium nitrite, and the Fe element-containing metal salt is ferrous oxide; the concentrations of the Na element-containing metal salt solution and the Fe element-containing metal salt solution are respectively 0.5-1mol/L, and the concentration of the precipitator is 0.1-1 mol/L; the volume ratio of the three solutions is as follows: 20% -30% -50%; the reaction temperature is 10-40 ℃.
5. The production method according to claim 3, characterized in that: in the step (2), the aging temperature is 40-100 ℃, and the aging time is 1-10H; the drying temperature is 60-100 ℃, and the drying time is 6-24H; the roasting temperature is 250 ℃ and 500 ℃, and the roasting time is 2-12H.
6. The production method according to claim 3, characterized in that: in the step (4), the ZSM-5 molecular sieve is immersed in the impregnating solution, the Na and Fe element metal oxide components in the impregnating solution are adhered on the molecular sieve body, namely in the pore channels, and the standing time is 16-24H.
7. The production method according to claim 3, characterized in that: in the step (4), the processing comprises the following steps: will be attached with Na-Fe 3 O 4 Roasting ZSM-5 molecular sieve of metal oxide at 250-500 deg.c for 8-12H), mechanically ball milling, pressing and sieving to obtain 20-80 mesh grains, and mixing homogeneously in a container to obtain the multifunctional composite Na-Fe3O4/ZSM-5 catalyst.
8. The application of the catalyst for directly preparing gasoline by carbon dioxide hydrogenation is characterized in that: the catalytic reaction for preparing gasoline by carbon dioxide hydrogenation is carried out in a fixed bed catalytic reaction tower, the catalyst is activated in an inert gas Na atmosphere before the reaction, then mixed gas of carbon dioxide and hydrogen is introduced for reaction, and finally the reaction product is cooled to room temperature and collected in a liquid phase.
9. Use of a catalyst according to claim 8, characterized in that: the activation temperature is 400 ℃ and 500 ℃, and the activation time is 5-12 hours.
10. Use of a catalyst according to claim 8, characterized in that: in the mixed gas of carbon dioxide and hydrogen, the molar ratio of the carbon dioxide to the hydrogen is 4: 1; the reaction conditions are as follows: the reaction temperature is 350-.
CN202210637755.7A 2022-06-13 2022-06-13 Preparation method and application of catalyst for directly preparing gasoline by carbon dioxide hydrogenation Pending CN114870886A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427672A (en) * 2023-10-20 2024-01-23 中南民族大学 For CO 2 Method for preparing catalyst for hydrogenation catalytic conversion into long-chain hydrocarbon and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427672A (en) * 2023-10-20 2024-01-23 中南民族大学 For CO 2 Method for preparing catalyst for hydrogenation catalytic conversion into long-chain hydrocarbon and application thereof

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