CN114471744B - Pretreatment method of iron-based catalyst and application thereof - Google Patents
Pretreatment method of iron-based catalyst and application thereof Download PDFInfo
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
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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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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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
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The application discloses a pretreatment method and application of an iron-based catalyst, wherein the pretreatment method at least comprises three steps of reduction, carbon monoxide treatment and re-reduction of the iron-based catalyst in sequence. The iron-based catalyst treated by the method can obviously increase CO 2 The application provides a new thought for the pretreatment process of the iron-based catalyst for preparing gasoline by hydrogenation of carbon dioxide.
Description
Technical Field
The application relates to a pretreatment method of an iron-based catalyst and application thereof, belonging to the field of catalysis.
Background
The conversion of carbon dioxide to prepare liquid fuel and high-value chemicals has potential significance in the fields of energy and chemical industry in China, and is beneficial to emission reduction of carbon dioxide and effective utilization of carbon dioxide. In addition, the hydrogen produced by electrolysis of water with renewable energy sources (water energy, solar energy, wind energy and the like) can be converted into liquid fuel and high-value chemicals, and the energy storage problem which always plagues the renewable energy sources can be solved, so that the process of preparing the liquid fuel and the high-value chemicals by hydrogenating the carbon dioxide plays an important role in future energy systems. Among the products, gasoline is an important transportation fuel, is most widely applied worldwide, has the most perfect storage and transportation infrastructure, and can realize the application of preparing gasoline by hydrogenating carbon dioxide, thereby having extremely great promotion effect on the popularization and utilization of renewable energy.
But due to CO 2 Is chemically inert to CO 2 Hydroconversion to lower carbon compounds such as methane, methanol, etc. is relatively easy, but conversion to higher carbon compounds is very challenging and there is a need to develop more efficient catalyst systems. CO 2 The studies on hydrogenation of highly selective synthetic gasoline hydrocarbons can be divided into two categories: one is through the reaction of an oxygen-containing intermediate species such as methanol; the other is via a Fischer-Tropsch (FTS) like reaction. At present, most of research works mainly adopt FTS-like reaction paths, namely CO 2 CO is generated by Reverse Water Gas Shift (RWGS) reaction, and then the FTS reaction occurs after CO hydrogenation. In either way, the single pass yield of carbon dioxide is to be further improved; among the numerous catalysts studied, the iron-based catalyst is taken as the most studied and cheapest Fischer-Tropsch catalyst, which is naturally an ideal candidate for preparing gasoline by carbon dioxide hydrogenation, but the currently studied iron-based catalyst for preparing gasoline by carbon dioxide hydrogenation still has the characteristics of low gasoline yield, insufficient induction period and stability of catalyst reaction, improves the yield of preparing gasoline by carbon dioxide hydrogenation, shortens the induction period of catalyst reaction and improves the stability of the catalystSex is a challenging problem for this study.
Disclosure of Invention
According to one aspect of the present application, there is provided a pretreatment method of an iron-based catalyst, which can significantly increase CO 2 The application provides a new thought for the pretreatment process of the iron-based catalyst for preparing gasoline by hydrogenation of carbon dioxide.
The application aims to provide a pretreatment method for preparing gasoline by carbon dioxide hydrogenation, and the iron-based catalyst pretreated by the process has higher reaction performance for preparing gasoline by carbon dioxide hydrogenation and good catalytic stability.
FeO formed in the process of reduction and reaction of iron-based catalyst for preparing gasoline by hydrogenation of carbon dioxide x 、FeC x The iron species are active species in the reaction of preparing gasoline by hydrogenating carbon dioxide, the existence forms and the proportions of the iron species are different, and the reactivity of the catalyst and the selectivity of hydrocarbon products are different. The iron-based catalyst is generally subjected to a reduction pretreatment process before the reaction of preparing gasoline by hydrogenating carbon dioxide, the reduction pretreatment process has an important influence on the generation of reactive iron active species, and the difference of the iron active species directly influences the catalytic performance of the catalyst, the distribution of hydrocarbon products and the like. For the conventional hydrogen reduction pretreatment process of the iron-based catalyst, the iron-based catalyst is usually reduced to zero-valent iron almost entirely, and FeO is gradually formed during the reaction x 、FeC x Species, such that the initial reaction period is caused by the formation of active species of the catalyst iron, and the length of the induction period directly influences the progress of the process. For iron-based catalysts, in particular in the presence of CO 2 In an iso-oxidizing atmosphere, the rate of formation of iron carbide after reduction of the catalyst is relatively slow. Therefore, in order to solve the problem, the application advances the formation of the active iron carbide species of the iron-based catalyst in the pretreatment process of reduction, and simultaneously realizes the controllable preparation of the iron carbide species, thus not only shortening the induction period of the reaction, but also increasingThe content of active species of the iron carbide is increased, so that the reactivity and the reaction stability of the catalyst are improved.
The pretreatment step of the present application may facilitate the formation of iron carbide as compared to the formation of iron carbide during the reaction, which may involve a number of reactions that are detrimental to the formation of iron carbide, such as the formation of carbon oxide, which is a competing reaction for the formation of iron carbide. The pretreatment process provided by the application is an in-situ pretreatment process, and the reaction of the raw material gas can be directly switched after the pretreatment is finished.
According to the pretreatment method of the iron-based catalyst, feC is finally formed x And the iron simple substance, and the active iron simple substance is easily oxidized to form FeO in the reaction process x Thus, in the reaction of carbon dioxide hydrogenation to gasoline, the active species is FeC x And FeO x . Wherein FeO is X Is a reverse water gas shift reaction (CO) 2 Hydrogenation to CO and water), feC X Is an active species for Fischer-Tropsch synthesis reactions (hydrogenation of CO to olefins and other hydrocarbon compounds). In the catalyst, two steps of reactions are series reactions, and generated olefin is converted on an acidic molecular sieve to generate gasoline.
The iron-based catalyst is subjected to hydrogen reduction to obtain an iron simple substance, then part of the iron simple substance reacts with carbon monoxide to obtain active iron carbide, and then the composition ratio of the iron carbide to the iron in the catalyst is regulated and controlled in a hydrogen treatment mode.
The application aims at CO 2 The pretreatment method of the iron-based multifunctional catalyst for preparing gasoline by hydrogenation refers to a treatment method of the catalyst through a reduction-carbonylation-re-reduction process before reaction, and comprises the following steps: 1) The reduction process and the re-reduction process of the pretreatment process refer to a reduction process of the iron-based catalyst under specific conditions in a reducing atmosphere containing hydrogen. The reducing atmosphere and conditions of the pre-treatment process may be the same or different from those of the re-reduction process. 2) The carbonylation process of the pretreatment process refers to a process of performing iron-based catalyst carbonylation under specific conditions in an atmosphere containing CO.
According to a first aspect of the present application, there is provided a pretreatment method of an iron-based catalyst, the pretreatment method comprising at least three steps of subjecting the iron-based catalyst to reduction, carbon monoxide treatment and re-reduction in this order.
Optionally, the iron-based catalyst comprises an active component and an auxiliary element;
the active component comprises Fe 3 O 4 ；
The auxiliary element is at least one selected from sodium, potassium, manganese, calcium, cobalt and copper.
Optionally, the auxiliary agent in the application is in the form of metal oxide or metal.
Optionally, the mass content of the auxiliary element in the iron-based catalyst is 0.01-20%.
Preferably, the mass content of the auxiliary element in the iron-based catalyst is 0.1-5%.
Optionally, the pretreatment method at least comprises the following steps:
(1) Reduction of iron-based catalysts
Reacting a raw material containing an iron-based catalyst in a reducing atmosphere to obtain a precursor I;
(2) Carbon monoxide treatment
Placing the precursor I obtained in the step (1) in an atmosphere I containing carbon monoxide, and reacting II to obtain a precursor II;
(3) Re-reduction
And (3) placing the precursor II obtained in the step (2) in a reducing atmosphere to react III, thus obtaining the pretreated iron-based catalyst.
Optionally, in the step (1) and the step (3), the reducing atmosphere includes hydrogen; the volume content of the hydrogen in the reducing atmosphere is 1-100%.
Preferably, the hydrogen is contained in the reducing atmosphere in a volume content of 5 to 100%.
Alternatively, the upper limit of the volume content of hydrogen in the reducing atmosphere is independently selected from 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, and the lower limit is independently selected from 1%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%.
Optionally, in the step (1) and the step (3), an inert gas is further included in the reducing atmosphere.
Optionally, the volume content of the inactive gas in the reducing atmosphere is 0.01-99%.
Alternatively, the upper limit of the volume content of the inactive gas in the reducing atmosphere is independently selected from 99%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and the lower limit is independently selected from 0.01%, 5%, 90%, 95%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%.
Optionally, the preparation method of the iron-based catalyst in the application comprises the following steps:
will contain Fe 3+ Source and Fe 2+ Hydrochloric acid is added into the raw materials of the source, and the alkali source is added at a constant speed under the stirring condition at 60 ℃. The acidic pH of the solution was adjusted to a pH of about 10. After the dripping is finished, stirring at constant temperature, and cooling to room temperature. After the reaction is finished, separating a deposition product by utilizing magnetic field adsorption, washing the deposition product to be neutral by deionized water, drying, grinding, tabletting and sieving (20-40 meshes) to obtain the auxiliary agent-Fe 3 O 4 And (5) standby.
Optionally, the alkali source is selected from sodium hydroxide.
Optionally, in the step (1) and the step (3), the conditions of the reaction I and the reaction III are: the reaction temperature is 200-500 ℃; the reaction pressure is 0.01-3.0 MPa; the reaction time is 4-24 hours; the space velocity of the reducing atmosphere is 1000-10000 ml.h -1 ·g Cat -1 。
Alternatively, the upper temperature limit of reaction I and reaction III is independently selected from 500 ℃, 400 ℃, 300 ℃, and the lower temperature limit is independently selected from 200 ℃, 400 ℃, 300 ℃.
Alternatively, the upper pressure limits of reaction I and reaction III are independently selected from 3MPa, 2.5MPa, 2MPa, 1.5MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05MPa, and the lower pressure limits are independently selected from 0.01MPa, 2.5MPa, 2MPa, 1.5MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05MPa.
Alternatively, the upper time limits of reactions I and III are independently selected from 24h, 20h, 18h, 14h, 10h, 6h, and the lower time limits are independently selected from 4h, 20h, 18h, 14h, 10h, 6h.
Alternatively, the upper space velocity limit of the reducing atmosphere of reaction I and reaction III is independently selected from 10000 ml.h -1 ·g Cat -1 、8000ml·h -1 ·g Cat -1 、6000ml·h -1 ·g Cat -1 、4000ml·h -1 ·g Cat -1 、2000ml·h -1 ·g Cat -1 The lower limit is independently selected from 1000 ml.h -1 ·g Cat -1 、8000ml·h -1 ·g Cat -1 、6000ml·h -1 ·g Cat -1 、4000ml·h -1 ·g Cat -1 、2000ml·h -1 ·g Cat -1 。
Optionally, in the step (1) and the step (3), the conditions of the reaction I and the reaction III are: the reaction temperature is 300-450 ℃; the reaction pressure is 0.1-2.0 MPa; the reaction time is 4-16 h; the space velocity of the reducing atmosphere is 2000-5000 ml.h -1 ·g Cat -1 。
Optionally, in the step (2), the conditions of reaction II are: the reaction temperature is 200-500 ℃; the reaction pressure is 0.01-3.0 MPa; the airspeed of atmosphere I is 1000-10000 ml.h -1 ·g Cat -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction time is 5-60 h.
Alternatively, the upper temperature limit of reaction II is independently selected from 500 ℃, 400 ℃, 300 ℃, and the lower temperature limit is independently selected from 200 ℃, 300 ℃, 400 ℃.
Alternatively, the upper pressure limit of reaction II is independently selected from 3MPa, 2MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05MPa, and the lower pressure limit is independently selected from 0.01MPa, 2MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05MPa.
Alternatively, the upper space velocity limit of the atmosphere I is independently selected from 10000 ml.h -1 ·g Cat -1 、8000ml·h -1 ·g Cat -1 、6000ml·h -1 ·g Cat -1 、4000ml·h -1 ·g Cat -1 、2000ml·h -1 ·g Cat -1 The lower limit is independently selected from 1000 ml.h -1 ·g Cat -1 、8000ml·h -1 ·g Cat -1 、6000ml·h -1 ·g Cat -1 、4000ml·h -1 ·g Cat -1 、2000ml·h -1 ·g Cat -1 。
Alternatively, the upper time limit of reaction II is independently selected from 60h, 50h, 40h, 30h, 20h, 10h, 8h, and the lower time limit is independently selected from 5h, 50h, 40h, 30h, 20h, 10h, 8h.
Optionally, in the step (2), the conditions of reaction II are: the reaction temperature is 300-400 ℃; the reaction pressure is 0.05-2.0 MPa; the airspeed of atmosphere I is 1000-3000 ml.h -1 ·g Cat -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction time is 6-30 h.
Optionally, in the step (2), the atmosphere I further includes an inert gas;
the volume content of the inactive gas in the atmosphere I is 0.01-70%.
Optionally, in the step (2), the upper limit of the volume content of the inactive gas in the atmosphere I is independently selected from 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, and the lower limit is independently selected from 0.01%, 60%, 50%, 40%, 30%, 20%, 10%, 5%.
According to a second aspect of the present application, there is also provided a pretreated iron-based catalyst, which is prepared according to the above pretreatment method.
Optionally, the pretreated iron-based catalyst comprises iron carbide and elemental iron;
wherein the mass content of the iron element in the pretreated iron-based catalyst is 10-70%.
Alternatively, the upper limit of the mass content of the iron element in the pretreated iron-based catalyst is independently selected from 70%, 60%, 50%, 40%, 30%, 20%, and the lower limit is independently selected from 10%, 60%, 50%, 40%, 30%, 20%.
Preferably, the mass content of the iron element in the pretreated iron-based catalyst is 30-50%.
Optionally, the molar ratio of the carbide of iron to the elemental iron is 5-95:95-5.
According to a third aspect of the present application there is also provided a method of producing gasoline, the method comprising at least: reacting a raw material gas II containing carbon dioxide and hydrogen in the presence of a catalyst IV to obtain gasoline;
the catalyst comprises an iron-based catalyst and a molecular sieve catalyst after pretreatment;
the pretreated iron-based catalyst is selected from at least one of the pretreated iron-based catalyst prepared according to the pretreatment method and the pretreated iron-based catalyst.
Optionally, the molecular sieve catalyst is selected from at least one of HZSM-5, HZSM-22, HZSM-23, MOR, MCM-22.
When the application is used for preparing gasoline, the iron-based active component of the pretreated catalyst is used for catalyzing the reaction of carbon dioxide and hydrogen to prepare a low-carbon olefin intermediate through reverse water vapor change; the molecular sieve active component is used for catalyzing low-carbon olefin to prepare gasoline.
Optionally, in the raw material gas II, the volume ratio of the hydrogen to the carbon dioxide is 1-5: 1.
optionally, the raw material gas II also comprises a gas A; the gas A is selected from C 1 ～C 4 At least one of an alkane and an inert gas; the volume content of the gas A in the raw material gas II is 0.01-10%.
Alternatively, the upper limit of the volume content of the gas a in the feed gas II is independently selected from 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, and the lower limit is independently selected from 0.01%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%.
Preferably, the C 1 ～C 4 The alkane of (2) is selected from methane.
Optionally, the inert gas includes nitrogen and an inert gas.
Alternatively, the conditions of reaction IV are: the reaction temperature is 280-380 ℃; the airspeed of the feed gas II is 1000-10000 mL.h -1 ·g FeCat -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction pressure is 0.1-5.0 MPa.
Alternatively, the upper space velocity limit of the feed gas II is independently selected from 10000 mL.h -1 ·g FeCat -1 、8000mL·h -1 ·g FeCat -1 、6000mL·h -1 ·g FeCat -1 、4000mL·h -1 ·g FeCat -1 、2000mL·h -1 ·g FeCat -1 The lower limit is independently selected from 1000 mL.h -1 ·g FeCat -1 、8000mL·h -1 ·g FeCat -1 、6000mL·h -1 ·g FeCat -1 、4000mL·h -1 ·g FeCat -1 、2000mL·h -1 ·g FeCat -1 。
In the present application, g FeCa Refers to the mass of the iron catalyst.
Alternatively, the upper pressure limit of the reaction IV is independently selected from 5MPa, 4MPa, 3MPa, 2MPa, 1MPa, 0.5MPa, and the lower pressure limit is independently selected from 0.1MPa, 4MPa, 3MPa, 2MPa, 1MPa, 0.5MPa.
In the application, the performance evaluation of the catalyst is carried out in a stainless steel fixed bed reactor (with the inner diameter of 14 mm), the granularity of the adopted iron-based catalyst particles is 20-40 meshes, and the catalyst bed layer is positioned at the constant temperature section of the heating furnace. The catalyst before reaction is treated by the reduction pretreatment process: at 250-500 ℃, 0.01-3.0 MPa and space velocity of reducing atmosphere of 1000-10000 ml.h -1 ·gCat -1 The reduction of the iron-based catalyst is carried out for 4 to 24 hours. After the reduction is finished, the reduction condition is switched to the carbonylation condition (comprising CO atmosphere, the temperature is 200-500 ℃, the pressure is 0.01-3.0 MPa, and the space velocity of the reduction atmosphere is 1000-5000 ml.h) -1 ·gCat -1 ) The carbonylation treatment of the catalyst is carried out for 5 to 60 hours, the re-reduction of the catalyst is carried out (250 to 500 ℃,0.01 to 3.0MPa, and the space velocity of the reducing atmosphere is 1000 to 10000 ml.h) -1 ·g Cat-1 The reduction of the iron-based catalyst is carried out for 4 to 30 hours). The catalyst is reduced and pretreated, and then is regulated to the reaction temperature at the speed of 1 ℃/min, and is switched into the reaction raw material gas (H) 2 /CO 2 /N 2 N, N 2 As an internal standard, H 2 /CO 2 The volume ratio is 0.5:1-4:1), and back pressure is carried out to the reaction pressure (0.1-3.0 MPa). The reaction products are analyzed on line by adopting gas chromatography, reaction tail gas is directly fed into a first gas chromatography to analyze all organic products on line by heat preservation, and then the products are cooled by a cold trap and fed into a second gas chromatography to carry out N-phase reaction 2 、CO 2 、CO、CH 4 Analysis was performed and reaction data were obtained after stabilization of the reaction.
The application has the beneficial effects that:
the pretreatment method of the iron-based catalyst provided by the application has higher reaction performance for preparing gasoline by hydrogenation of carbon dioxide, can shorten the induction period of the reaction, and shows good catalytic stability.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The molecular sieve in the application is purchased from a molecular sieve catalyst of Nanka university, and the salt compound is purchased from Shanghai A Ding Huaxue Co. Catalyst test chromatography uses Agilent 7890B to analyze product hydrocarbons, shimadzu 8A to analyze gas composition, etc.
In the present application, CO 2 Conversion from N 2 The internal standard method is used for calculating, the selectivity of hydrocarbon products is calculated by adopting an area normalization method by using the areas of the chromatographic peaks after the correction, and the specific calculation method is as follows:
CO 2 the conversion was calculated as follows:
CO 2 conversion (%) = (CO) 2,in -CO 2,out )/CO 2,in х100％
The CO selectivity calculation formula is as follows:
CO selectivity (%) =co out /(CO 2,in -CO 2,out )х100％
In the above, CO 2,in And CO 2,out Represents the mole fraction of CO in the inlet and outlet of the reactor, CO out Representing the mole fraction of CO in the reactor outlet.
The product hydrocarbon selectivity is calculated as follows:
selectivity of hydrocarbon product of carbon number i (selectivity calculated as mole percent of carbon number) = (carbon number of hydrocarbon product of carbon number i/carbon number of all hydrocarbon products) ×100%
Example 1
Preparing an iron-based catalyst:
8.78g FeCl 3 ·6H 2 O and 3.48g FeCl 2 ·4H 2 O was mixed with 30mL of water to form an iron salt solution, and 1.42mL of 12.1mol/L HCl solution was added. About 100mL of 1.5mol/LNaOH solution was added at a constant rate at 60℃with stirring. The acidic pH of the solution was adjusted to a pH of about 10 within about 1.5 hours. After the dripping is finished, stirring for 1h at constant temperature, and cooling to room temperature. After the reaction is finished, separating a deposition product by using magnetic field adsorption, washing the deposition product to be neutral by using deionized water, drying, grinding, tabletting and sieving (20-40 meshes) to obtain Na 2 O-Fe 3 O 4 And (5) standby.
HZSM-5 preparation:
HZSM-5 (SiO) purchased from molecular sieve works at university of south China 2 /Al 2 O 3 =160) was calcined at 500 ℃ for 4h, and the sample was ground, tabletted and sieved to obtain HZSM-5 for use.
Pretreatment and evaluation of the catalyst:
na to be prepared 2 O-Fe 3 O 4 And HZSM-5 are packed in the reactor in layers, and the catalyst bed layer is sequentially packed with Na from top to bottom of the reactor 2 O-Fe 3 O 4 And the HZSM-5 catalyst, wherein a quartz sand inert material isolation layer is contained between the two catalyst bed components, and the mass ratio of the inert material isolation layer to the composite catalyst active component is 0.1. The catalyst loading was 1g, na 2 O-Fe 3 O 4 And HZSM-5 were charged with 0.5g each.
Through normal pressure and pure H 2 350℃、6000ml·h -1 ·g Cat -1 Reducing for 4h; normal pressure, CO 300 ℃, 2000 ml.h -1 ·g Cat -1 Treating for 4H under normal pressure and pure H 2 350℃、6000ml·h -1 ·g Cat -1 And the reaction is reduced for 8 hours. After the completion of the reduction, the temperature was adjusted to 320℃at a rate of 1℃per minute, and the reaction mixture was switched to the reaction mixture gas (H) 2 /CO 2 /N 2 N, N 2 As an internal standard, H 2 /CO 2 The volume ratio is 4/1, N 2 4% of the catalyst at 330℃and 3.0MPa,600 ml.g Cat -1 ·h -1 The performance of the synthesis gas direct synthesis gasoline for 100 hours is shown in Table 1.
Comparative example 1
The procedure is as in example 1, except that the pretreatment conditions are changed to normal pressure, pure H 2 350℃、6000ml·h -1 ·g Cat-1 Reduction for 4 hours, the reaction performance test procedure and conditions of comparative example 1 were the same as in example 1.
The reaction results of the catalysts pretreated in example 1 and comparative example 1 for use in the reaction of carbon dioxide hydrogenation to gasoline are shown in table 1.
TABLE 1 Na 2 O-Fe 3 O 4 HZSM-5 catalyzed CO 2 Reaction performance of hydrogenation to gasoline
As can be seen from example 1 and comparative example 1, CO in comparative example 1 2 The conversion rate reached the maximum (33.1%) after 10 hours of reaction, and the selectivity of the gasoline fraction was 72%. Then gradually inactivating, and reducing the reaction time to 27.5% after 100 hours, wherein the activity loss reaches 17%; from the reaction performance of example 1, it was found that the reaction time was 2 hours to reach a stable value, the conversion was stabilized at about 35.5% and the selectivity of the gasoline fraction was 73.4% within 100 hours of the reaction time. As can be seen by comparison, the catalyst pretreated by the method of the application is hydrogenated by carbon dioxide for 100 hoursIn the reaction test for preparing gasoline, the reaction performance of the catalyst is improved, the induction period of the reaction is shortened, and the stability of the catalyst is improved.
Example 2
The procedure is as in example 1, except that Na is prepared 2 O-Fe 3 O 4 Mn auxiliary agent is added to obtain Mn-Na 2 O-Fe 3 O 4 Catalyst, mn-Na 2 O-Fe 3 O 4 The preparation of the catalyst is prepared by adopting an isovolumetric impregnation method, and comprises the following specific steps:
10g of Na prepared by the method of example 1 was weighed 2 O-Fe 3 O 4 Samples, according to the content of the needed auxiliary agent, are prepared into corresponding Mn salt solution (1.0 mol/L Mn (NO) 3 ) 2 Solution), 10g Na 2 O-Fe 3 O 4 Immersing the sample in the prepared salt solution (5 mL) in equal volume, stirring, standing for 20h, oven drying at 60deg.C, roasting at 480 deg.C for 6h, grinding, tabletting, and sieving (20-40 mesh) to obtain Mn-Na 2 O-Fe 3 O 4 。
Measured Mn-Na 2 O-Fe 3 O 4 The reaction properties of HZSM-5 catalyzed carbon dioxide hydrogenation to gasoline are shown in Table 2.
Example 3
The procedure is as in example 2, except that Na is prepared 2 O-Fe 3 O 4 Adding Co auxiliary agent to obtain Co-Na 2 O-Fe 3 O 4 Catalyst, co-Na 2 O-Fe 3 O 4 The reaction properties of HZSM-5 catalyzed carbon dioxide hydrogenation to gasoline are shown in Table 2.
Co-Na in this example 2 O-Fe 3 O 4 Preparation procedure and conditions of the catalyst are the same as Mn-Na 2 O-Fe 3 O 4 The preparation steps and conditions of (a) are those of Mn (NO) 3 ) 2 The solution is changed into CO (NO) 3 ) 2 A solution.
Example 4
The procedure of example 1 is followed except that Na is prepared 2 O-Fe 3 O 4 N applied in the stepThe aOH is replaced by KOH to obtain K-Fe 3 O 4 。
Measured K-Fe 3 O 4 The reaction properties of HZSM-5 catalyzed carbon dioxide hydrogenation to gasoline are shown in Table 2.
TABLE 2 auxiliary M modified M-Fe 3 O 4 HZSM-5 catalyzed CO 2 Reaction performance of hydrogenation to gasoline
As can be seen from the results of Table 2, regardless of Na 2 O-Fe 3 O 4 Mn and Co auxiliary agents or K auxiliary agents replacing Na are added in the alloy to be applied to M-Fe 3 O 4 HZSM-5 catalyzed CO 2 The hydrogenation gasoline preparation reaction shows good reaction performance and catalytic reaction stability.
Example 5
The catalyst used in this example was the same as in example 1, and the catalyst pretreatment process step and the reaction step for producing gasoline by hydrogenating carbon dioxide were the same as in example 1, except that the catalyst pretreatment process was changed to 3.0MPa, 95% Ar/H 2 500℃、10000ml·h -1 ·g Cat -1 Reducing for 24h;3.0MPa, CO 400 ℃, 5000 ml.h -1 ·g Cat -1 Treating for 12H,2.0MPa, 95% Ar/H 2 ,400℃、5000ml·h -1 ·g Cat -1 And the reaction is further reduced for 16 hours. The catalytic carbon dioxide hydrogenation reaction time is changed to 60 hours.
The catalytic carbon dioxide hydrogenation gasoline preparation reaction performance of the pretreatment catalyst under the above conditions is shown in table 3.
Example 6
The catalyst used in this example was the same as in example 1, and the catalyst pretreatment process step and the reaction step for producing gasoline by hydrogenating carbon dioxide were the same as in example 1, except that the catalyst pretreatment process was changed to be carried out under a pressure of 0.01MPa and 5% N 2 /H 2 400℃、10000ml·h -1 ·g Cat -1 Reducing for 24h;2.0MPa, 50% Ar/CO 300 ℃, 1000 ml.h -1 ·g Cat -1 The treatment was carried out for 60 hours,1.0MPa、45％Ar/H 2 ,400℃、2000ml·h -1 ·g Cat -1 and the reaction is reduced for 8 hours. The catalytic carbon dioxide hydrogenation reaction time is changed to 60 hours.
The catalytic carbon dioxide hydrogenation gasoline preparation reaction performance of the pretreatment catalyst under the above conditions is shown in table 3.
Example 7
The catalyst used in this example was the same as in example 1, and the catalyst pretreatment process step and the reaction step for producing gasoline by hydrogenating carbon dioxide were the same as in example 1, except that the catalyst pretreatment process was changed to 1.0MPa, 50% Ar/H 2 200℃、2000ml·h -1 ·g Cat -1 Reducing for 24h;0.01MPa, 70% Ar/CO500 ℃, 1000 ml.h -1 ·g Cat -1 Treating for 48h,1.0MPa, 95% N 2 /H 2 ,300℃、2000ml·h -1 ·g Cat -1 And the reaction is reduced for 8 hours. The catalytic carbon dioxide hydrogenation reaction time is changed to 60 hours.
The catalytic carbon dioxide hydrogenation gasoline preparation reaction performance of the pretreatment catalyst under the above conditions is shown in table 3.
TABLE 3 Na 2 O-Fe 3 O 4 HZSM-5 catalyzed CO 2 Reaction performance of hydrogenation to gasoline
As can be seen from Table 3, the pretreated catalyst maintained good catalytic performance, catalytic stability and shorter reaction induction period over the range of pretreatment conditions examined.
Example 8
The catalyst used in this example was the same as in example 1, and the catalyst pretreatment process step and the reaction step for producing gasoline by hydrogenating carbon dioxide were the same as in example 1, except that the reaction temperature for catalyzing carbon dioxide was changed to 280, 300 ℃, 320 ℃, 350 ℃, 380 ℃. The results of the catalytic reaction were changed to those of the reaction for 10 hours, and the reaction properties are shown in Table 4.
Example 9
The catalyst used in this example was the same as in example 1, and the catalyst pretreatment process step and the reaction step for producing gasoline by hydrogenating carbon dioxide were the same as in example 1, except that the reaction pressure for catalyzing carbon dioxide was changed to 0.1MPa, 1.0MPa, 3.0MPa, 5.0MPa. The results of the catalytic reaction were changed to those of the reaction for 10 hours, and the reaction properties are shown in Table 4.
Example 10
The catalyst used in this example was the same as in example 1, and the catalyst pretreatment process step and the reaction step for producing gasoline by hydrogenating carbon dioxide were the same as in example 1, except that the reaction space velocity for catalyzing carbon dioxide was changed to 1000, 3000, 5000, 8000, 10000 mL.h -1 ·g FeCat -1 . The results of the catalytic reaction were changed to those of the reaction for 10 hours, and the reaction properties are shown in Table 4.
TABLE 4 reaction Performance of the catalytic hydrogenation of carbon dioxide to gasoline under different reaction conditions
As can be seen from the results in Table 4, the pretreated catalyst of the application has excellent reaction performance for preparing gasoline by hydrogenating carbon dioxide in the examined reaction temperature, pressure and space velocity ranges, and the proper conditions and CO are controlled 2 The conversion rate can reach more than 30%, the selectivity of CO in the product is controlled below 15%, and the selectivity of gasoline fraction hydrocarbon in hydrocarbon products can be controlled above 70%.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (6)
1. A method for preparing gasoline is characterized in that,
the method at least comprises the following steps: reacting a raw material gas II containing carbon dioxide and hydrogen in the presence of a catalyst IV to obtain gasoline;
the catalyst comprises an iron-based catalyst and a molecular sieve catalyst after pretreatment;
the iron-based catalyst comprises an active component and an auxiliary element;
the active component comprises Fe 3 O 4 ；
The auxiliary element is at least one of sodium, potassium, manganese, calcium, copper and cobalt;
the pretreatment comprises the following steps:
(1) Reduction of iron-based catalysts
Reacting a raw material containing an iron-based catalyst in a reducing atmosphere to obtain a precursor I;
(2) Carbon monoxide treatment
Placing the precursor I obtained in the step (1) in an atmosphere I containing carbon monoxide, and reacting II to obtain a precursor II;
(3) Re-reduction
Placing the precursor II obtained in the step (2) in a reducing atmosphere to react III, so as to obtain a pretreated iron-based catalyst;
the reducing atmosphere consists of hydrogen and inactive gas;
the volume content of the hydrogen in the reducing atmosphere is 1-100%;
the volume content of the inactive gas in the atmosphere I is 0.01-70%;
in the step (1) and the step (3), the conditions of the reaction I and the reaction III are independently selected from: the reaction temperature is 200-500 o C, performing operation; the reaction pressure is 0.01-3.0 MPa; the reaction time is 4-24 hours; the space velocity of the reducing atmosphere is 1000-10000 ml.h -1 ·g Cat -1 ；
In the step (2), the conditions of reaction II are: the reaction temperature is 200-500 o C, performing operation; the reaction pressure is 0.01-3.0 MPa; the airspeed of atmosphere I is 1000-10000 ml.h -1 ·g Cat -1 The method comprises the steps of carrying out a first treatment on the surface of the During the reactionThe time is 5-60 h.
2. The method of claim 1, wherein the pretreated iron-based catalyst comprises iron carbide and elemental iron;
wherein the mass content of the iron element in the pretreated iron-based catalyst is 10-70%.
3. The method of claim 2, wherein the molar ratio of iron carbide to elemental iron is 5-95:95-5.
4. The method according to claim 1, wherein in the raw material gas II, the volume ratio of hydrogen to carbon dioxide is 1 to 5:1.
5. the method according to claim 1, wherein the feed gas II further comprises a gas a; the gas A is selected from C 1 ~C 4 At least one of an alkane and an inert gas; the volume content of the gas A in the raw material gas II is 0.01-10%.
6. The method according to claim 1, wherein the conditions of reaction IV are: the reaction temperature is 280-380 o C, performing operation; the airspeed of the raw material gas II is 1000-10000 mL.h -1 ·g FeCat -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction pressure is 0.1-5.0 MPa.
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