CN114471744A - Pretreatment method and application of iron-based catalyst - Google Patents

Pretreatment method and application of iron-based catalyst Download PDF

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CN114471744A
CN114471744A CN202011266126.5A CN202011266126A CN114471744A CN 114471744 A CN114471744 A CN 114471744A CN 202011266126 A CN202011266126 A CN 202011266126A CN 114471744 A CN114471744 A CN 114471744A
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iron
reaction
based catalyst
catalyst
gas
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CN114471744B (en
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葛庆杰
位健
张继新
孙剑
方传艳
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Zhuhai Fuyi Energy Technology Co ltd
Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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

Abstract

The application discloses a pretreatment method and application of an iron-based catalyst. The iron-based catalyst treated by the method can obviously increase CO2The invention provides a new idea for the pretreatment process of the iron-based catalyst for preparing gasoline by carbon dioxide hydrogenation.

Description

Pretreatment method and application of iron-based catalyst
Technical Field
The application relates to a pretreatment method and application of an iron-based catalyst, belonging to the field of catalysis.
Background
The method for preparing the liquid fuel and the high-value chemical products by converting the carbon dioxide has potential significance in the fields of energy and chemical industry in China, is beneficial to emission reduction of the carbon dioxide, and is beneficial to effective utilization of the carbon dioxide as a resource. In addition, hydrogen produced by electrolyzing water by using renewable energy sources (water energy, solar energy, wind energy and the like) and carbon dioxide can be converted into liquid fuel and high-value chemicals, and the problem of energy storage which always troubles the renewable energy sources can be solved, so that the process of producing the liquid fuel and the high-value chemicals by hydrogenating the carbon dioxide plays an important role in a future energy system. Among many products, gasoline is an important transportation fuel, is most widely applied worldwide, has the most perfect storage and transportation infrastructure, and has a great promoting effect on the popularization and utilization of renewable energy sources undoubtedly if the application of gasoline prepared by carbon dioxide hydrogenation can be realized.
But due to CO2Is chemically inert to CO2Hydrogenation to lower carbon compounds such as methane, methanol, etc. is relatively easy, but conversion to higher carbon containing compounds is very challenging and more efficient catalyst systems need to be developed. CO 22The research on the hydrogenation high-selectivity synthesis of gasoline hydrocarbon compounds can be divided into two categories: one is through the reaction of oxygen-containing intermediate species such as methanol; the other is via a Fischer-Tropsch synthesis (FTS) like reaction. Currently, most of the research work mainly employs FTS-like reaction pathways, i.e., CO2CO is generated through a Reverse Water Gas Shift (RWGS) reaction, and then the FTS reaction is generated after the CO is hydrogenated. In any way, the single-pass yield of the carbon dioxide needs to be further improved; among a plurality of catalysts researched, the iron-based catalyst which is the most researched and the cheapest Fischer-Tropsch catalyst is naturally an ideal candidate for preparing the gasoline catalyst by the carbon dioxide hydrogenation, but the iron-based catalyst for preparing the gasoline by the carbon dioxide hydrogenation still has the characteristics of low gasoline yield and insufficient induction period and stability of catalyst reaction, and the problems of improving the yield of the gasoline by the carbon dioxide hydrogenation, shortening the induction period of the catalyst reaction and improving the stability of the catalyst are quite challenging in the research.
Disclosure of Invention
According to one aspect of the present application, there is provided a method for pretreating an iron-based catalyst to significantly increase CO2The invention provides a new idea for the pretreatment process of the iron-based catalyst for preparing gasoline by carbon dioxide hydrogenation.
The invention aims to provide a pretreatment method for preparing gasoline by carbon dioxide hydrogenation, and an iron-based catalyst pretreated by the process shows high reactivity of preparing gasoline by carbon dioxide hydrogenation and simultaneously shows good catalytic stability.
FeO formed in the reduction and reaction process of the iron-based catalyst for preparing gasoline by carbon dioxide hydrogenationx、FeCxThe iron species are active species for the reaction of preparing gasoline by hydrogenating carbon dioxide, the existence forms and the proportions of the iron species are different, and the reaction performance of the catalyst and the selectivity of hydrocarbon products are different. The iron-based catalyst generally undergoes a reduction pretreatment process before the reaction of preparing gasoline by carbon dioxide hydrogenation, 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 conventional hydrogen reduction pretreatment processes of iron-based catalysts, the iron-based catalysts are usually almost completely reduced to zero-valent iron, and FeO is gradually formed during the reaction processx、FeCxThe species, so that the reaction is induced in the early stage by the formation of the active species of the catalyst iron, and the length of the induction period directly influences the process. For iron-based catalysts, especially in the presence of CO2In an oxidizing atmosphere, the speed of the catalyst for forming iron carbide after reduction is relatively slow. Therefore, aiming at the problem, the invention advances the formation of the active iron carbide species of the iron-based catalyst in the reduction pretreatment process to the pretreatment process, and simultaneously realizes the controllable preparation of the iron carbide species, thereby not only shortening the induction period of the reaction, but also increasing the content of the active iron carbide species, and further increasing the reaction performance and the reaction stability of the catalyst.
The pretreatment step in the present invention makes it easier to form iron carbide than during the reaction, because the atmosphere during the reaction is more complex and may contain many 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 invention 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 iron-based catalyst pretreatment method of the present application, FeC is finally formedxAnd iron simple substance, and the active iron simple substance is easily oxidized to generate FeO in the reaction processxThus, in the reaction process for the hydrogenation of carbon dioxide to produce gasoline, the active species is FeCxAnd FeOx. In which FeO is presentXIs a reverse water gas shift reaction (CO)2Reaction of hydrogenation to CO and water), FeCXIs an active species of Fischer-Tropsch synthesis reaction (CO is hydrogenated to generate hydrocarbon compounds such as olefin). In the catalyst, the two-step reaction is a series reaction, and the generated olefin is converted on an acidic molecular sieve to generate gasoline.
The iron-based catalyst is firstly reduced by hydrogen to obtain an iron simple substance, then part of the iron simple substance reacts with carbon monoxide to obtain active species iron carbide, and then the composition ratio of the iron carbide and the iron in the catalyst is regulated and controlled by a hydrogen treatment mode.
Invention for CO2The pretreatment method of the iron-based multifunctional catalyst for preparing gasoline by hydrogenation refers to a treatment method of the catalyst after reduction-carbonylation-reducibility process before reaction, which comprises the following steps: 1) the reduction process and the re-reduction process of the pretreatment process refer to an iron-based catalyst reduction process performed under specific conditions in a reducing atmosphere containing hydrogen. The reducing atmosphere and conditions of the reduction process and the re-reduction process of the pretreatment process may be the same or different. 2) The carbonylation process of the pretreatment process refers to an iron-based catalyst carbonylation process carried out under specific conditions in an atmosphere containing CO.
According to a first aspect of the present application, there is provided a method of pretreating an iron-based catalyst, the method comprising at least three steps of reducing the iron-based catalyst, treating with carbon monoxide, and reducing again in that order.
Optionally, the iron-based catalyst comprises an active component and an auxiliary element;
the active component comprises Fe3O4；
The auxiliary element is at least one of sodium, potassium, manganese, calcium, cobalt and copper.
Optionally, the auxiliaries herein are present in the form of metal oxides or metals.
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 comprises at least the following steps:
(1) iron-based catalyst reduction
Reacting a raw material containing an iron-based catalyst in a reducing atmosphere to obtain a precursor I;
(2) carbon monoxide treatment
Putting the precursor I obtained in the step (1) into an atmosphere I containing carbon monoxide, and reacting II to obtain a precursor II;
(3) is reduced again
And (3) placing the precursor II obtained in the step (2) in a reducing atmosphere, and reacting the precursor II with the precursor III to obtain the pretreated iron-based catalyst.
Optionally, in the step (1) and the step (3), the reducing atmosphere comprises hydrogen; the volume content of the hydrogen in the reducing atmosphere is 1-100%.
Preferably, the volume content of the hydrogen in the reducing atmosphere is 5-100%.
Optionally, 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 inert gas in the reducing atmosphere is 0.01-99%.
Alternatively, the upper limit of the volume content of the inert 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%.
Alternatively, the preparation method of the iron-based catalyst in the present application comprises:
will contain Fe3+Source and Fe2+Adding hydrochloric acid into raw materials of the source, and adding an alkali source at a constant speed under the condition of stirring at 60 ℃. The acidic pH of the solution was adjusted to about pH 10. After the dropwise addition, stirring at constant temperature, and cooling to room temperature. After the reaction is finished, separating the deposition product by 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-Fe3O4And (5) standby.
Optionally, the alkali source is selected from sodium hydroxide.
Alternatively, in the step (1) and the step (3), the conditions of the reaction I and the reaction III are both: the reaction temperature is 200-500 ℃; the reaction pressure is 0.01-3.0 MPa; the reaction time is 4-24 h; the space velocity of the reducing atmosphere is 1000-10000 ml.h-1·gCat -1。
Alternatively, the upper temperature limit for reaction I and reaction III is independently selected from 500 deg.C, 400 deg.C, 300 deg.C, and the lower temperature limit is independently selected from 200 deg.C, 400 deg.C, 300 deg.C.
Alternatively, the upper pressure limits for 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 limits are independently selected from 0.01MPa, 2.5MPa, 2MPa, 1.5MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05 MPa.
Alternatively, the upper time limit of reaction I and reaction III is independently selected from 24h, 20h, 18h, 14h, 10h, 6h, and the lower time limit is independently selected from 4h, 20h, 18h, 14h, 10h, 6 h.
Alternatively, the upper space velocity limit of the reducing atmosphere for reaction I and reaction III is independently selected from 10000ml · h-1·gCat -1、8000ml·h-1·gCat -1、6000ml·h-1·gCat -1、4000ml·h-1·gCat -1、2000ml·h-1·gCat -1The lower limit is independently selected from 1000 ml. h-1·gCat -1、8000ml·h-1·gCat -1、6000ml·h-1·gCat -1、4000ml·h-1·gCat -1、2000ml·h-1·gCat -1。
Alternatively, in the step (1) and the step (3), the conditions of the reaction I and the reaction III are both: 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·gCat -1。
Alternatively, in the step (2), the conditions of the reaction II are: the reaction temperature is 200-500 ℃; the reaction pressure is 0.01-3.0 MPa; the space velocity of the atmosphere I is 1000-10000 ml.h-1·gCat -1(ii) a The reaction time is 5-60 h.
Alternatively, the upper temperature limit of reaction II is independently selected from 500 deg.C, 400 deg.C, 300 deg.C, and the lower temperature limit is independently selected from 200 deg.C, 300 deg.C, 400 deg.C.
Alternatively, the upper pressure limit for reaction II is independently selected from 3MPa, 2MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05MPa and the lower limit is independently selected from 0.01MPa, 2MPa, 1MPa, 0.5MPa, 0.1MPa, 0.05 MPa.
Optionally, the upper space velocity limit of the atmosphere I is independently selected from 10000ml h-1·gCat -1、8000ml·h-1·gCat -1、6000ml·h-1·gCat -1、4000ml·h-1·gCat -1、2000ml·h-1·gCat -1The lower limit is independently selected from 1000 ml. h-1·gCat -1、8000ml·h-1·gCat -1、6000ml·h-1·gCat -1、4000ml·h-1·gCat -1、2000ml·h-1·gCat -1。
Alternatively, the upper time limit of the 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, 8 h.
Alternatively, in the step (2), the conditions of the reaction II are: the reaction temperature is 300-400 ℃; the reaction pressure is 0.05-2.0 MPa; the space velocity of the atmosphere I is 1000-3000 ml.h-1·gCat -1(ii) a The reaction time is 6-30 h.
Optionally, in the step (2), the atmosphere I further comprises an inert gas;
the volume content of the inert gas in the atmosphere I is 0.01-70%.
Optionally, in the step (2), the upper limit of the volume content of the inert 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 prepared according to the above pretreatment method.
Optionally, the pretreated iron-based catalyst comprises iron carbide and iron simple substance;
wherein the mass content of the iron element in the pretreated iron-based catalyst is 10-70%.
Optionally, 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 iron carbide to the iron simple substance 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 at least comprising: reacting the feed gas II containing carbon dioxide and hydrogen in the presence of a catalyst to obtain gasoline;
the catalyst comprises a pretreated iron-based catalyst and a molecular sieve catalyst;
the pretreated iron-based catalyst is at least one selected from the group consisting 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 catalyst 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 moisture change; the active component of the molecular sieve is used for catalyzing low-carbon olefin to prepare gasoline.
Optionally, in the raw material gas II, the volume ratio of hydrogen to carbon dioxide is 1-5: 1.
optionally, the raw material gas II further comprises a gas A; the gas A is selected from C1～C4At least one of an alkane, an inert gas; the volume content of the gas A in the feed gas II is 0.01-10%.
Alternatively, the upper limit of the volume content of 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, said C1～C4The alkane of (a) is selected from methane.
Optionally, the inert gas comprises nitrogen and an inert gas.
Optionally, the conditions of reaction IV are: the reaction temperature is 280-380 ℃; the space velocity of the feed gas II is 1000-10000mL & h-1·gFeCat -1(ii) a The reaction pressure is 0.1-5.0 MPa.
Alternatively, the upper space velocity limit of the feed gas II is independently selected from 10000mL h-1·gFeCat -1、8000mL·h-1·gFeCat -1、6000mL·h-1·gFeCat -1、4000mL·h-1·gFeCat -1、2000mL·h-1·gFeCat -1The lower limit is independently selected from 1000 mL. h-1·gFeCat -1、8000mL·h-1·gFeCat -1、6000mL·h-1·gFeCat -1、4000mL·h-1·gFeCat -1、2000mL·h-1·gFeCat -1。
In this application, gFeCaRefers to the mass of the iron catalyst.
Alternatively, the upper pressure limit of reaction IV is independently selected from 5MPa, 4MPa, 3MPa, 2MPa, 1MPa, 0.5MPa, and the lower limit is independently selected from 0.1MPa, 4MPa, 3MPa, 2MPa, 1MPa, 0.5 MPa.
In the application, the performance evaluation of the catalyst is carried out in a stainless steel fixed bed reactor (the inner diameter is 14mm), the granularity of the adopted iron-based catalyst particles is 20-40 meshes, and a catalyst bed layer is positioned in a constant temperature section of a heating furnace. The catalyst before reaction is treated by the reduction pretreatment process of the invention: at a temperature of 250 ℃ and 500 ℃, 0.01 to 3.0MPa and a space velocity of 1000 to 10000 ml.h in a reducing atmosphere-1·gCat-1Reducing the iron-based catalyst for 4-24 hours under the condition of (1). After the reduction is finished, the reduction condition is switched to the carbonylation condition (containing CO atmosphere, 200-500 ℃, 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, and the re-reduction of the catalyst is carried out (250 ℃ C., 0.01 to 3.0MPa, and the space velocity of the reducing atmosphere is 1000 to 10000 ml.h)-1·gCat-1Reducing the iron-based catalyst for 4 to 30 hours). After the catalyst is subjected to reduction pretreatment, the reaction temperature is adjusted to 1 ℃/min, and the reaction raw material gas (H) is switched to2/CO2/N2Mixed gas of (2), N2As internal standard, H2/CO2The 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 product is analyzed on line by gas chromatography, the reaction tail gas is directly fed into the first gas chromatography for on-line analysis of all organic products after heat preservation, and then the products are cooled by a cold trapThen enters a second gas chromatography pair N2、CO2、CO、CH4And (4) analyzing, and obtaining reaction data after the reaction is stable.
The beneficial effects that this application can produce include:
the iron-based catalyst pretreatment method provided by the invention has higher reactivity for preparing gasoline by carbon dioxide hydrogenation, can shorten the induction period of the reaction, and shows good catalytic stability.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The molecular sieve of the invention is purchased from molecular sieve catalysts of southern Kao university, and the salt compounds are purchased from Shanghai Aladdin chemical Co. The catalyst test chromatogram adopts Agilent 7890B to analyze the product hydrocarbons, Shimadzu 8A to analyze the gas composition and the like.
In this application, CO2Conversion from N2Calculating by an internal standard method, and calculating the selectivity of the hydrocarbon product by using the area normalization method according to the chromatographic peak areas after respective correction, wherein the specific calculation method is as follows:
CO2the conversion calculation formula is as follows:
CO2conversion (%) ═ CO2,in-CO2,out)/CO2,inх100％
The CO selectivity calculation formula is as follows:
CO selectivity (%) ═ COout/(CO2,in-CO2,out)х100％
In the above formula, CO2,inAnd CO2,outRespectively representing the mole fraction of CO in the inlet and outlet of the reactor, COoutRepresenting the mole fraction of CO in the reactor outlet.
The calculation formula for the product hydrocarbon selectivity is as follows:
selectivity (selectivity in mole percent of carbon number) of hydrocarbon product with carbon number i ═ x 100% (carbon number of hydrocarbon product with carbon number i/carbon number of hydrocarbon product in total)
Example 1
Preparing an iron-based catalyst:
8.78g FeCl3·6H2O and 3.48g FeCl2·4H2O 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 a 1.5mol/L NaOH solution was added at a constant rate with stirring at 60 ℃. The acidic pH of the solution was adjusted to around pH 10 in about 1.5 h. After the dropwise addition, stirring at constant temperature for 1h, and cooling to room temperature. After the reaction is finished, separating the deposition product by magnetic field adsorption, washing the deposition product to be neutral by deionized water, drying, grinding, tabletting and sieving (20-40 meshes) to obtain Na2O-Fe3O4And (5) standby.
HZSM-5 preparation:
HZSM-5 (SiO) purchased from molecular sieves works of southern Kaiki university2/Al2O3160) was calcined at 500 ℃ for 4h, and the sample was milled, tableted and sieved to give HZSM-5 for use.
Catalyst pretreatment and evaluation:
prepared Na2O-Fe3O4And HZSM-5 are filled in the reactor layer by layer, and Na is filled in the catalyst bed layer from top to bottom in sequence in the reactor2O-Fe3O4And the HZSM-5 catalyst, a quartz sand inert material isolating layer is arranged between the two catalyst bed components, and the mass ratio of the inert material isolating layer to the composite catalyst active component is 0.1. The catalyst loading was 1g, Na2O-Fe3O40.5g of HZSM-5 was charged.
Under normal pressure, pure H2 350℃、6000ml·h-1·gCat -1Reducing for 4 h; normal pressure, CO 300 deg.C, 2000 ml.h-1·gCat -1Treating for 4H at normal pressure with pure H2 350℃、6000ml·h-1·gCat -1And reducing for 8 h. After the reduction is finished, the temperature is adjusted to 320 ℃ at the speed of 1 ℃/min, and the reaction raw material gas (H) is switched to2/CO2/N2Mixed gas of (2), N2As internal standard, H2/CO2The volume ratio is 4/1, N24%) of catalyst at 330 deg.C, 3.0MPa,6000ml gCat -1·h-1The performance of the gasoline directly synthesized from the synthesis gas 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 and pure H2 350℃、6000ml·h-1·gCat-1Reduction was carried out for 4 hours, and the reaction performance test procedure and conditions of comparative example 1 were the same as those of example 1.
The results of the use of the catalysts pretreated in example 1 and comparative example 1 in the reaction of producing gasoline by hydrogenation of carbon dioxide are shown in table 1.
TABLE 1.Na2O-Fe3O4HZSM-5 catalyzed CO2Reaction performance of hydrogenation gasoline
Figure BDA0002776097570000091
As can be seen from example 1 and comparative example 1, CO in comparative example 12The conversion reached the highest (33.1%) after 10 hours of reaction and the selectivity of the gasoline fraction was 72%. Then gradually deactivating, reducing the reaction time to 27.5% within 100 hours, and the activity loss reaches 17%; as can be seen from the reaction performance of example 1, a stable value is achieved within 2 hours of the reaction, the conversion is stabilized at about 35.5% within 100 hours of the reaction, and the gasoline fraction selectivity is 73.4%. The comparison shows that the catalyst pretreated by the method not only improves the reaction performance of the catalyst, but also shortens the induction period of the reaction and improves the stability of the catalyst in a reaction test of preparing gasoline by hydrogenating carbon dioxide for 100 hours.
Example 2
The procedure is as in example 1, except that Na is prepared2O-Fe3O4Adding Mn auxiliary agent to obtain Mn-Na2O-Fe3O4Catalyst, Mn-Na2O-Fe3O4The preparation method adopts an isometric immersion method, and comprises the following specific steps:
10g of Na prepared by the method of example 1 were weighed2O-Fe3O4Samples are prepared into corresponding Mn salt solution (1.0mol/L Mn (NO) according to the content composition of the required additives3)2Solution), 10g of Na2O-Fe3O4Soaking the sample in the prepared salt solution (5mL) in equal volume, stirring, standing for 20h, oven drying at 60 deg.C, roasting at 480 deg.C for 6h, grinding, tabletting, and sieving (20-40 mesh) to obtain Mn-Na2O-Fe3O4。
Measured Mn-Na2O-Fe3O4The reactivity of the/HZSM-5 catalyst for the hydrogenation of carbon dioxide to gasoline is shown in Table 2.
Example 3
The procedure is as in example 2, except that Na is prepared2O-Fe3O4Adding Co additive to obtain Co-Na2O-Fe3O4Catalyst, determination of Co-Na2O-Fe3O4The reactivity of the/HZSM-5 catalyst for the hydrogenation of carbon dioxide to gasoline is shown in Table 2.
Co-Na in this example2O-Fe3O4The preparation steps and conditions of the catalyst are the same as those of Mn-Na2O-Fe3O4Except that Mn (NO) is added3)2The solution is changed into CO (NO)3)2And (3) solution.
Example 4
The auxiliary element in this example is K, the procedure is as in example 1, except that Na is to be prepared2O-Fe3O4Replacing NaOH applied in the step with KOH to obtain K-Fe3O4。
Measured K-Fe3O4The reactivity of the/HZSM-5 catalyst for the hydrogenation of carbon dioxide to gasoline is shown in Table 2.
TABLE 2 auxiliary M modified M-Fe3O4HZSM-5 catalyzed CO2Reactivity of hydrogenated gasoline
Figure BDA0002776097570000111
As can be seen from the results in Table 2, no matter Na2O-Fe3O4Mn and Co additives are added, and K additives for replacing Na are also added, and the method is applied to M-Fe3O4HZSM-5 catalyzed CO2The hydrogenation gasoline reaction shows good reaction performance and catalytic reaction stability.
Example 5
The catalyst used in this example was the same as in example 1, except that the pretreatment of the catalyst was changed to 3.0MPa and 95% Ar/H, and the pretreatment of the catalyst and the reaction of hydrogenating carbon dioxide to gasoline were the same as in example 12 500℃、10000ml·h-1·gCat -1Reducing for 24 hours; 3.0MPa, CO 400 deg.C, 5000 ml.h-1·gCat -1Treating for 12H at 2.0MPa and 95% Ar/H2,400℃、5000ml·h-1·gCat -1And reducing for 16 h. The reaction time of catalytic carbon dioxide hydrogenation is changed to 60 hours.
The catalytic carbon dioxide hydrogenation gasoline reactivity of the conditioned pretreated catalyst is shown in Table 3.
Example 6
The catalyst used in this example was the same as in example 1, except that the pretreatment of the catalyst was changed to 0.01MPa and 5% N, and the steps of the pretreatment and the reaction for producing gasoline by hydrogenation of carbon dioxide were the same as in example 12/H2 400℃、10000ml·h-1·gCat -1Reducing for 24 hours; 2.0MPa, 50% Ar/CO 300 deg.C, 1000 ml.h-1·gCat -1Treating for 60H at 1.0MPa and 45% Ar/H2,400℃、2000ml·h-1·gCat -1And reducing for 8 h. The reaction time of catalytic carbon dioxide hydrogenation is changed to 60 hours.
The catalytic carbon dioxide hydrogenation gasoline reactivity of the conditioned pretreated catalyst is shown in Table 3.
Example 7
The catalyst used in this example was the same as in example 1, and the pretreatment process and the reaction for hydrogenation of carbon dioxide to gasoline were the same as in example 1 except that the catalyst was usedThe pretreatment process of the agent is changed into 1.0MPa and 50 percent Ar/H2 200℃、2000ml·h-1·gCat -1Reducing for 24 hours; 0.01MPa, 70% Ar/CO500 deg.C, 1000 ml.h-1·gCat -1Treating for 48h at 1.0MPa and 95% N2/H2,300℃、2000ml·h-1·gCat -1And reducing for 8 h. The reaction time of catalytic carbon dioxide hydrogenation is changed to 60 hours.
The catalytic carbon dioxide hydrogenation gasoline reactivity of the conditioned pretreated catalyst is shown in Table 3.
TABLE 3.Na2O-Fe3O4HZSM-5 catalyzed CO2Reactivity of hydrogenated gasoline
Figure BDA0002776097570000121
As can be seen from Table 3, the pretreated catalyst can maintain good catalytic performance, catalytic stability and short reaction induction period within the range of the considered pretreatment conditions.
Example 8
The catalyst used in this example was the same as in example 1, and the pretreatment process and the reaction for hydrogenation of carbon dioxide to gasoline 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 test results of the catalytic reaction were changed to those of 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 pretreatment process and the reaction for hydrogenation of carbon dioxide to gasoline 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, and 5.0 MPa. The test results of the catalytic reaction were changed to those of 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, the catalyst pretreatment step and the reaction step for producing gasoline by hydrogenation of carbon dioxideThe same procedure as in example 1 was repeated except that the space velocity of the reaction for catalyzing carbon dioxide was changed to 1000, 3000, 5000, 8000, 10000 mL. h-1·gFeCat -1. The test results of the catalytic reaction were changed to those of 10 hours, and the reaction properties are shown in Table 4.
TABLE 4 reactivity of CO 2 catalytic hydrogenation to gasoline under different reaction conditions
Figure BDA0002776097570000131
As can be seen from the results in Table 4, the catalysts pretreated by the method of the invention all show excellent reactivity of the carbon dioxide hydrogenation to gasoline within the range of the reaction temperature, the pressure and the space velocity, and the proper conditions are controlled, and CO is prepared2The conversion rate can reach more than 30 percent, the CO selectivity in the product is controlled below 15 percent, and the selectivity of the gasoline fraction hydrocarbon in the hydrocarbon product can be controlled above 70 percent.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The pretreatment method of the iron-based catalyst is characterized by at least sequentially carrying out three steps of reduction, carbon monoxide treatment and re-reduction on the iron-based catalyst.
2. The pretreatment method according to claim 1, wherein the iron-based catalyst comprises an active component and an auxiliary element;
the active component comprises Fe3O4；
The auxiliary element is at least one of sodium, potassium, manganese, calcium, copper and cobalt.
3. The pretreatment method according to claim 1, comprising at least the steps of:
(1) iron-based catalyst reduction
Reacting a raw material containing an iron-based catalyst in a reducing atmosphere to obtain a precursor I;
(2) carbon monoxide treatment
Putting the precursor I obtained in the step (1) into an atmosphere I containing carbon monoxide, and reacting II to obtain a precursor II;
(3) is reduced again
And (3) placing the precursor II obtained in the step (2) in a reducing atmosphere, and reacting the precursor II with the precursor III to obtain the pretreated iron-based catalyst.
4. The pretreatment method according to claim 3, wherein 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%.
5. The pretreatment method according to claim 4, wherein in the step (1) and the step (3), an inert gas is further included in the reducing atmosphere.
6. The pretreatment method according to claim 3, wherein in the step (1) and the step (3), conditions of the reaction I and the reaction III are independently selected from the group consisting of: the reaction temperature is 200-500 ℃; the reaction pressure is 0.01-3.0 MPa; the reaction time is 4-24 h; the space velocity of the reducing atmosphere is 1000-10000 ml.h-1·gCat -1；
In the step (2), the conditions of the reaction II are as follows: the reaction temperature is 200-500 ℃; the reaction pressure is 0.01-3.0 MPa; the space velocity of the atmosphere I is 1000-10000 ml.h-1·gCat -1(ii) a The reaction time is 5-60 h;
preferably, in the step (2), the atmosphere I further comprises an inert gas;
the volume content of the inert gas in the atmosphere I is 0.01-70%.
7. A pretreated iron-based catalyst prepared according to the pretreatment method of any one of claims 1 to 6.
8. The pretreated iron-based catalyst of claim 7, wherein the pretreated iron-based catalyst comprises iron carbide and elemental iron;
wherein the mass content of iron element in the pretreated iron-based catalyst is 10-70%;
preferably, the molar ratio of the iron carbide to the iron simple substance is 5-95: 95-5.
9. A process for the preparation of gasoline, characterized in that it comprises at least: reacting the feed gas II containing carbon dioxide and hydrogen in the presence of a catalyst to obtain gasoline;
the catalyst comprises a pretreated iron-based catalyst and a molecular sieve catalyst;
the pretreated iron-based catalyst is selected from at least one of the pretreated iron-based catalyst prepared by the pretreatment method according to any one of claims 1 to 6, and the pretreated iron-based catalyst according to claim 7 or 8.
10. The method according to claim 9, wherein in the raw material gas II, the volume ratio of hydrogen to carbon dioxide is 1-5: 1;
preferably, the raw material gas II also comprises a gas A; the gas A is selected from C1～C4At least one of an alkane, an inert gas; the volume content of the gas A in the feed gas II is 0.01-10%;
preferably, the strip of reaction IVThe parts are as follows: the reaction temperature is 280-380 ℃; the space velocity of the feed gas II is 1000-10000 mL.h-1·gFeCat -1(ii) a The reaction pressure is 0.1-5.0 MPa.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB926009A (en) * 1959-04-13 1963-05-15 South African Coal Oil Gas Improvements in and relating to iron catalysts
JP3010314B2 (en) * 1995-07-31 2000-02-21 コリア リサーチ インスティチュート オブ ケミカル テクノロジイ Hydrocarbon preparation method
CN1248494A (en) * 1998-09-23 2000-03-29 中国科学院山西煤炭化学研究所 Process for preparing skeleton iron catalyst used in Fischer-Tropsch synthesis
CN1651136A (en) * 2004-11-30 2005-08-10 中国科学院山西煤炭化学研究所 Reduction method of syrup state bed Fischer Tropsch synthesis iron base catalyst
US20120245236A1 (en) * 2011-03-26 2012-09-27 Suib Steven L Fischer-tropsch catalysts containing iron or cobalt selective towards higher hydrocarbons
US20160045901A1 (en) * 2013-03-19 2016-02-18 Korea Institute Of Energy Research Iron-based catalyst and method for preparing the same and use thereof
WO2018049938A1 (en) * 2016-09-19 2018-03-22 中国科学院大连化学物理研究所 Method for directly preparing gasoline fraction hydrocarbons by carbon dioxide hydrogenation
CN108435239A (en) * 2018-05-10 2018-08-24 江南大学 A kind of catalyst and the preparation method and application thereof of coproduction alkene and aromatic hydrocarbons
CN108816294A (en) * 2018-06-21 2018-11-16 浦江思欣通科技有限公司 A kind of fixed bed Fischer-Tropsch iron catalyst activating pretreatment method
WO2019192079A1 (en) * 2018-04-02 2019-10-10 国家能源投资集团有限责任公司 SUPPORTED ε/ε' IRON CARBIDE CATALYST FOR USE IN FISCHER-TROPSCH SYNTHESIS REACTION, PREPARATION METHOD FOR CATALYST, AND METHOD FOR FISCHER-TROPSCH SYNTHESIS

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB926009A (en) * 1959-04-13 1963-05-15 South African Coal Oil Gas Improvements in and relating to iron catalysts
JP3010314B2 (en) * 1995-07-31 2000-02-21 コリア リサーチ インスティチュート オブ ケミカル テクノロジイ Hydrocarbon preparation method
CN1248494A (en) * 1998-09-23 2000-03-29 中国科学院山西煤炭化学研究所 Process for preparing skeleton iron catalyst used in Fischer-Tropsch synthesis
CN1651136A (en) * 2004-11-30 2005-08-10 中国科学院山西煤炭化学研究所 Reduction method of syrup state bed Fischer Tropsch synthesis iron base catalyst
US20120245236A1 (en) * 2011-03-26 2012-09-27 Suib Steven L Fischer-tropsch catalysts containing iron or cobalt selective towards higher hydrocarbons
US20160045901A1 (en) * 2013-03-19 2016-02-18 Korea Institute Of Energy Research Iron-based catalyst and method for preparing the same and use thereof
WO2018049938A1 (en) * 2016-09-19 2018-03-22 中国科学院大连化学物理研究所 Method for directly preparing gasoline fraction hydrocarbons by carbon dioxide hydrogenation
WO2019192079A1 (en) * 2018-04-02 2019-10-10 国家能源投资集团有限责任公司 SUPPORTED ε/ε' IRON CARBIDE CATALYST FOR USE IN FISCHER-TROPSCH SYNTHESIS REACTION, PREPARATION METHOD FOR CATALYST, AND METHOD FOR FISCHER-TROPSCH SYNTHESIS
CN108435239A (en) * 2018-05-10 2018-08-24 江南大学 A kind of catalyst and the preparation method and application thereof of coproduction alkene and aromatic hydrocarbons
CN108816294A (en) * 2018-06-21 2018-11-16 浦江思欣通科技有限公司 A kind of fixed bed Fischer-Tropsch iron catalyst activating pretreatment method

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
WANG ET AL.: "Synthesis of stable and low-CO2 selective e-iron carbide Fischer-Tropsch catalysts", 《SCIENCE ADVANCES》, pages 1 - 6 *
ZHANG J等: "The evolution of Fe phase of a fused iron catalyst during reduction and Fischer-Tropsch synthesis", 《CATALYSIS SCIENCE & TECHNOLOGY》, vol. 7, no. 16, pages 3626 - 3636 *
王向辉等: "费托合成催化剂还原技术研究", 《洁净煤技术》, vol. 19, no. 5, pages 54 - 59 *
王玲玉等: "合成气制低碳烯烃铁催化剂活性相的研究进展", 《化工进展》, vol. 38, no. 11, pages 4949 - 4955 *
王翀: "合成气直接制取低碳烯烃催化剂的研究", 《中国优秀博士学位论文》 *

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