CN115475637B - Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof - Google Patents

Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof Download PDF

Info

Publication number
CN115475637B
CN115475637B CN202110668294.5A CN202110668294A CN115475637B CN 115475637 B CN115475637 B CN 115475637B CN 202110668294 A CN202110668294 A CN 202110668294A CN 115475637 B CN115475637 B CN 115475637B
Authority
CN
China
Prior art keywords
catalyst
solution
reaction
preparation
fischer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110668294.5A
Other languages
Chinese (zh)
Other versions
CN115475637A (en
Inventor
庞颖聪
陶跃武
李剑锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN202110668294.5A priority Critical patent/CN115475637B/en
Publication of CN115475637A publication Critical patent/CN115475637A/en
Application granted granted Critical
Publication of CN115475637B publication Critical patent/CN115475637B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C07C2527/22—Carbides
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a catalyst for preparing olefin by Fischer-Tropsch synthesis, a preparation method and application thereof. The catalyst comprises a composite material, an oxide of alkaline metal A and an oxide of a carrier Z, wherein the composite material comprises graphite, metal carbide and metal oxide, and metals in the composite material are Fe and Ni. The catalyst is used for preparing olefin by Fischer-Tropsch synthesis, and has the advantages of fast reaction heat removal, difficult temperature runaway and high weight selectivity of target product olefin.

Description

Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing olefin by Fischer-Tropsch synthesis, a preparation method and application thereof.
Background
Fischer-Tropsch synthesis is CO and H 2 Under the action of catalyst, the complex reaction system with hydrocarbon product as main product. Generally, it is the CO hydrogenation and carbon chain growth reaction. Is an important method for converting and utilizing coal.
The Fischer-Tropsch catalysts commonly used at present are divided into two main categories in terms of the main active components: fe and Co. The Fe-based catalyst is classified into a precipitated Fe catalyst, a sintered Fe catalyst, and an oxide mixed fused Fe catalyst, and depending on the preparation method and the auxiliary agent used, the Fe-based catalyst may be used in a fischer-tropsch fluidized bed process at a high temperature (above 300 ℃) or a fischer-tropsch fixed bed (slurry bed) process at a low temperature (below 280 ℃), and the active phase of the Fe-based catalyst is generally considered to be iron carbide carbonized by synthesis gas, for example, a preparation of a fused iron type catalyst for fischer-tropsch synthesis is mentioned in patent CN1704161a, and a precipitated iron catalyst for a fluidized bed is mentioned in patent CN1695804 a. The Co catalyst is generally an impregnation load type, and the main active element Co is dispersed on the surface of a carrier, so that the Co catalyst is mostly used for producing saturated heavy hydrocarbons by a low-temperature Fischer-Tropsch process and is used for producing heavy hydrocarbons by low-temperature Fischer-Tropsch synthesis. Ni which is in the same family as Fe and Co has extremely strong hydrogenation performance after being reduced into a metallic state by hydrogen, and is used as a main catalyst for preparing methane from synthesis gas, for example, patent CN110339855A discloses a nickel-based catalyst for preparing methane from synthesis gas. For Ni-based catalyst for preparing methane from synthesis gas, the active phase is generally considered to be metal simple substance phase reduced by hydrogen, and the reaction condition is controlled in the process of preparing methane from synthesis gas, so that the catalyst deactivation caused by carbonization of metal Ni is avoided. There are some attempts to use a fixed bed for high temperature fischer-tropsch synthesis to make light olefins from synthesis gas, but because the synthesis gas conversion reaction is a strong exothermic reaction, when using a fixed bed, the heat removal in the reactor is difficult, the temperature is easy to fly, and the catalyst is easy to deactivate, and all the attempts are stopped at the laboratory stage. The fluidized bed can well overcome the problems existing in the fixed bed, but the catalysts for the fluidized bed prepared by the iron melting method and the catalysts for the fluidized bed prepared by the precipitation method have the defect that the selectivity of olefin mainly used as chemical raw materials does not have great advantages compared with the selectivity of alkane mainly used as fuel at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing olefin by Fischer-Tropsch synthesis, and a preparation method and application thereof. When the catalyst is used for preparing olefin by Fischer-Tropsch synthesis, the catalyst has the advantages of quick reaction heat removal, difficult temperature runaway and target product olefin (C) 2 -C 20 ) High weight selectivity.
In a first aspect of the invention, there is provided a catalyst for the preparation of olefins by Fischer-Tropsch synthesis, the catalyst comprising a composite material, an oxide of a basic metal A and an oxide of a support Z, wherein the composite material comprises graphite, a metal carbide and a metal oxide, and the metals in the composite material are Fe and Ni.
Further, the alkaline metal A comprises at least one of potassium and sodium. The Z comprises at least one of Si and Ti.
Further, the atomic ratio of Fe to a is 100:1-10; the atomic ratio of Fe to Z is 100:100-500.
Further, in the composite material, the proportion of Fe, ni, C, O is 100:5-20:150-300:35-70.
In a second aspect, the present invention provides a method for preparing the catalyst according to the first aspect, comprising the steps of:
s1, dissolving ferric salt, nickel salt, an auxiliary agent and a soluble carbon source in water (preferably deionized water) to obtain a solution I;
s2, stirring and heating the solution I to volatilize and concentrate the solution to obtain precursor powder II;
s3, mixing and pulping the precursor powder II, an aqueous solution of alkali metal A and an oxide sol of a carrier Z to obtain slurry III;
s4, drying the slurry III, and roasting under inert gas to obtain the catalyst.
Further, in step S1, the iron salt, nickel salt may be an iron salt, a nickel salt, which is conventional in the art, such as selected from iron nitrate, nickel nitrate, iron carbonate, nickel chloride, iron citrate, and the like.
Further, in the step S1, the ratio of the iron salt, the nickel salt, the auxiliary agent and the soluble carbon source is 100:5-20:280-360:100-300.
Further, in step S1, the auxiliary agent is glycine. The soluble carbon source is at least one selected from sucrose, fructose, maltose or glucose.
Further, in the step S1, the molar concentration of the obtained solution I is 0.05-2.5mol/L.
In step S2, the heating is performed at a temperature above 100 ℃, so that the purposes of volatilizing and concentrating the solution are achieved.
Further, in step S3, the alkaline metal a includes at least one of potassium and sodium; the carrier Z comprises at least one of Si and Ti.
Further, the iron salt and alkali metal added are such that the atomic ratio of Fe to A in the resulting catalyst is 100:1-10; the iron salt and carrier Z added satisfy the atomic ratio of Fe to carrier Z of 100 in the obtained catalyst: 100-500.
Further, in step S4, the drying is preferably spray drying, and the inlet temperature of the spray drying is 180-220 ℃ and the outlet temperature is 120-140 ℃.
Further, in step S4, the inert gas is at least one of common inert gases such as nitrogen and helium. The roasting temperature is 700-1000 ℃, and the roasting time is 3-15h.
In a third aspect the present invention provides the use of a catalyst according to the first aspect or a catalyst prepared by a process according to the second aspect in the preparation of olefins by Fischer-Tropsch synthesis.
The use is for the production of olefins by contacting synthesis gas with a catalyst according to the first aspect or a catalyst produced by a process according to the second aspect.
The application employs a fluidized bed reactor.
H in the synthesis gas 2 The molar ratio of the catalyst to CO is 0.5 to 5.0; and/or the reaction pressure is 1.0-8.0MPa; and/or the reaction temperature is 240-370 ℃; and/or the volume space velocity of the synthesis gas is 600-3000 hours -1 。
Compared with the prior art, the invention has the following advantages:
1. the catalyst of the invention is used for preparing olefin by Fischer-Tropsch synthesis, and has the advantages of quick reaction heat removal, difficult temperature runaway and olefin (C) 2 -C 20 ) High selectivity.
2. The Fe-based catalyst of the prior art is usually in the form of an oxide and must be subjected to H 2 The high-temperature treatment reduces the Fe into metallic Fe, and then the metallic Fe is carbonized by using synthesis gas or CO gas to prepare the low-carbon olefin serving as an active catalyst. The catalyst adopts a soluble carbon source, directly connects metal by carbon bond for forming, directly reacts, and reasonably controls the contents of metal carbide and graphite, so that the obtained catalyst is more beneficial to being used in the preparation of olefin by Fischer-Tropsch synthesis reaction.
3. Ni, which has extremely strong hydrogenation properties and is considered unsuitable for the production of non-methane organic hydrocarbons, is directly partially carbonized with a soluble carbon source, while retaining suitable hydrogenation activity, and carbonized with Fe to form a surface of a composite material more conducive to the formation of unsaturated olefins.
Drawings
FIG. 1 is an SEM image of a catalyst prepared according to example 1;
FIG. 2 is an SEM image of the catalyst prepared in comparative example 2;
FIG. 3 is an SEM image of the catalyst prepared in comparative example 3/comparative example 5.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to facilitate understanding of the present invention, the present invention is exemplified by the following examples. It will be apparent to those skilled in the art that the examples are merely to aid in the understanding of the present invention and should not be construed as a specific limitation thereof. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values.
SEM pictures of products in the embodiment of the invention adopt Philips company ESEM XL30 scanning electron microscope to observe the appearance of the catalyst, and Kratos Ultra DLD X ray photoelectron spectroscopy of Shimadzu company is adopted to analyze the composition of surface elements of the catalyst.
Example 1
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and sucrose containing 2mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I to volatilize and concentrate the solution, and obtaining mixed precursor powder II after reaction; dissolving 0.05mol KOH in water to obtain solution, mixing with precursor powder II and SiO 3mol 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then enter under nitrogen atmosphereRoasting at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 250 O 40 )(K 2 O) 2.5 (SiO 2 ) 300 SEM characterization of the catalyst is shown in figure 1. From fig. 1 it is evident that the appearance of the catalyst is a graphitized layer-wrapped microsphere.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reactions were run for 300 hours and 2000 hours, respectively.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Example 2
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and sucrose containing 2mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing the solution, concentrating the solution, and reacting to obtain mixed precursor powder II; dissolving 0.05mol of NaOH in water to prepare a solution, mixing the solution with precursor powder II and 3mol of SiO 2 35wt% silica sol was mixed and addedStirring and pulping a certain amount of water at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 250 O 40 )(Na 2 O) 2.5 (SiO 2 ) 300 SEM characterization of the catalyst is similar to figure 1.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Example 3
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and sucrose containing 2mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing the solution, concentrating the solution, and reacting to obtain mixed precursor powder II; dissolving 0.05mol KOH in water to obtain solution, mixing withPrecursor powder II and a catalyst containing 3mol of TiO 2 Mixing 35wt% of Ti sol, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 250 O 40 )(K 2 O) 2.5 (TiO 2 ) 300 SEM characterization of the catalyst is similar to figure 1.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Example 4
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and maltose containing 2mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing, concentrating and reversing the solutionObtaining mixed precursor powder II after reaction; dissolving 0.03mol of KOH and 0.02mol of NaOH in water to prepare a solution, mixing the solution with precursor powder II and SiO 3mol 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 250 O 40 )(K 2 O) 1.5 (Na 2 O) 1.0 (SiO 2 ) 300 SEM characterization of the catalyst is similar to figure 1.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Example 5
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and a catalyst containing2mol of fructose of carbon is dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing the solution, concentrating the solution, and reacting to obtain mixed precursor powder II; dissolving 0.05mol of NaOH in water to prepare a solution, mixing the solution with precursor powder II and 3mol of SiO 2 35wt% silica sol and containing 1mol of TiO 2 Mixing 35wt% of Ti sol, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 250 O 40 )(Na 2 O) 2.5 (SiO 2 ) 300 (TiO 2 ) 100 SEM characterization of the catalyst is similar to figure 1.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 1
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and sucrose containing 0.5mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing the solution, concentrating the solution, and reacting to obtain mixed precursor powder II; dissolving 0.05mol KOH in water to obtain solution, mixing with precursor powder II and SiO 3mol 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 60 O 130 )(K 2 O) 2.5 (SiO 2 ) 300 。
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours and 2000 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 2
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and sucrose containing 2mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing the solution, concentrating the solution, and reacting to obtain mixed precursor powder II; dissolving 0.05mol KOH in water to obtain solution, mixing with precursor powder II and SiO 3mol 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in air atmosphere at 800 deg.c for 8 hr to obtain catalyst particle with Fe composition 100 Ni 10 K 5 Si 300 O 762.5 SEM characterization of the catalyst is shown in figure 2. It can be seen from fig. 2 that the calcination at high temperature in air causes the catalyst to be powdered, indicating that the catalyst is not only surface-coated with graphitized carbon layer, but also a considerable portion of carbide in the bulk.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 3
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, preparing a mixed solution I with the concentration of 0.5 mol/L; taking a solution containing 4.5mol NH 3 20wt% ammonia water was added dropwise to the solution I to obtain Fe (OH) 3 And Ni (OH) 2 Filtering and washing to obtain a fresh precipitate mixture II; dissolving 0.05mol KOH in water to obtain a solution, mixing the solution with the mixture II and containing 3mol SiO 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in air atmosphere at 800 deg.c for 8 hr to obtain catalyst particle with Fe composition 100 Ni 10 K 5 Si 300 O 762.5 SEM characterization of the catalyst is shown in figure 3. From fig. 3, it is evident that the comparative catalyst is a microsphere-shaped oxide sphere, which is clearly distinguished from the catalyst sphere containing the carbide and carbon composite of the embodiment of fig. 1.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 4
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, preparing a mixed solution I with the concentration of 0.5 mol/L; taking a solution containing 4.5mol NH 3 20wt% ammonia water was added dropwise to the solution I to obtain Fe (OH) 3 And Ni (OH) 2 Filtering and washing to obtain a fresh precipitate mixture II; dissolving 0.05mol KOH in water to obtain a solution, mixing the solution with the mixture II and containing 3mol SiO 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle with Fe composition 100 Ni 10 K 5 Si 300 O 762.5 。
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual reaction)Volume space velocity) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 5
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, preparing a mixed solution I with the concentration of 0.5 mol/L; taking a solution containing 4.5mol NH 3 20wt% ammonia water was added dropwise to the solution I to obtain Fe (OH) 3 And Ni (OH) 2 Filtering and washing to obtain a fresh precipitate mixture II; dissolving 0.05mol KOH in water to obtain a solution, mixing the solution with the mixture II and containing 3mol SiO 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in air atmosphere at 800 deg.c for 8 hr to obtain catalyst particle with Fe composition 100 Ni 10 K 5 Si 300 O 762.5 SEM characterization of the catalyst is shown in figure 3.
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
the catalyst is subjected to reduction pretreatment
The reduction conditions are as follows: the temperature is 450 DEG C
Pressure of 1.0MPa
Catalyst loading (actual volumetric space velocity of reaction) 1000 hours -1
Reducing gas H 2
The time for the reduction was 12 hours and,
then switching to the synthesis condition to carry out the synthesis reaction,
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (molar) H2/co=1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 6
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O、0.1molNi(NO 3 ) 2 ·6H 2 O, 3.2mol of glycine and 3.5mol of sucrose containing carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I, volatilizing the solution, concentrating the solution, and reacting to obtain mixed precursor powder II; dissolving 0.05mol KOH in water to obtain solution, mixing with precursor powder II and SiO 3mol 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 Ni 10 C 320 O 20 )(K 2 O) 2.5 (SiO 2 ) 300 。
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
after the catalyst is filled into the reactor, N is used for 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reaction was run for 300 hours.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
Comparative example 7
1) Preparation of the catalyst:
taking 0.5mol of Fe 2 (NO 3 ) 3 ·9H 2 O, 3.2mol of glycine and sucrose containing 2mol of carbon are dissolved in water to prepare a mixed solution I with the concentration of 0.5 mol/L; stirring and heating the solution I to volatilize and concentrate the solution, and obtaining mixed precursor powder II after reaction; dissolving 0.05mol KOH in water to obtain solution, mixing with precursor powder II and SiO 3mol 2 Mixing the silica sol with 35wt% of the mixture, adding a certain amount of water, stirring and pulping at a high speed to obtain slurry III with the solid content of 35 wt%; spray drying and forming the slurry III, wherein the spraying condition is that the inlet temperature is 200 ℃ and the outlet temperature is 130 ℃; then roasting in nitrogen atmosphere at 800 deg.c for 8 hr to obtain catalyst particle, and through X-ray photoelectron spectrum analysis, the catalyst has the composition of (Fe 100 C 250 O 36 )(K 2 O) 2.5 (SiO 2 ) 300 。
2) Catalyst evaluation:
reactor specification:a millimeter fluidized bed reactor;
catalyst loading: 50 g;
catalyst is filled into the reactionAfter the device, use N 2 Purging the air in the reactor, and switching to synthetic reaction conditions to start reaction;
the synthesis reaction conditions are as follows:
the reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
Catalyst loading (actual volume space velocity of reaction) 1500 hours -1
Synthesis gas mixture ratio (mol) H 2 /CO＝1.5/1
The reactions were run for 300 hours, respectively.
The experimental results of the synthetic reaction of the catalyst obtained are shown in Table 1.
TABLE 1
/>

Claims (9)

1. A catalyst for the preparation of olefins by fischer-tropsch synthesis, characterized in that: the catalyst comprises a composite material, an oxide of alkaline metal A and an oxide of a carrier Z, wherein the composite material comprises graphite, metal carbide and metal oxide, and metals in the composite material are Fe and Ni;
in the composite material, the proportion of Fe, ni, C, O is 100:5-20:150-300:35-70 in terms of atomic ratio;
the alkaline metal A comprises at least one of potassium and sodium; the Z comprises at least one of Si and Ti;
the catalyst is prepared according to a preparation method comprising the following steps:
s1, dissolving ferric salt, nickel salt, an auxiliary agent and a soluble carbon source in water to obtain a solution I;
s2, stirring and heating the solution I to volatilize and concentrate the solution to obtain precursor powder II;
s3, mixing and pulping the precursor powder II with an aqueous solution of alkali metal A and an oxide sol of a carrier Z to obtain slurry III;
s4, drying the slurry III, and roasting under inert gas to obtain the catalyst;
in the step S1, the auxiliary agent is glycine;
in step S1, the soluble carbon source is at least one selected from sucrose, fructose, maltose and glucose.
2. The catalyst of claim 1, wherein: the atomic ratio of Fe to alkaline metal A is 100:1-10; the atomic ratio of Fe to Z is 100:100-500.
3. A process for preparing a catalyst for the preparation of olefins according to any of claims 1-2 comprising the steps of:
s1, dissolving ferric salt, nickel salt, an auxiliary agent and a soluble carbon source in water to obtain a solution I;
s2, stirring and heating the solution I to volatilize and concentrate the solution to obtain precursor powder II;
s3, mixing and pulping the precursor powder II with an aqueous solution of alkali metal A and an oxide sol of a carrier Z to obtain slurry III;
s4, drying the slurry III, and roasting under inert gas to obtain the catalyst;
in the step S1, the auxiliary agent is glycine;
in step S1, the soluble carbon source is at least one selected from sucrose, fructose, maltose and glucose.
4. A method according to claim 3, characterized in that: in the step S1, the proportion of the ferric salt, the nickel salt, the auxiliary agent and the soluble carbon source is 100:5-20:280-360:100-300.
5. A method according to claim 3, characterized in that: in step S1, the molar concentration of the obtained solution I is 0.05-2.5mol/L.
6. A method according to claim 3, characterized in that: in the step S4, the drying is spray drying, and the inlet temperature of the spray drying is 180-220 ℃ and the outlet temperature is 120-140 ℃.
7. A method according to claim 3, characterized in that: in the step S4, the roasting temperature is 700-1000 ℃ and the roasting time is 3-15h.
8. Use of the catalyst of any one of claims 1-2 or the catalyst prepared according to the process of any one of claims 3-7 for the preparation of olefins by fischer-tropsch synthesis.
9. The use according to claim 8, characterized in that: the application adopts a fluidized bed reactor, and the reaction conditions are as follows: h in synthesis gas 2 The molar ratio of the catalyst to CO is 0.5 to 5.0; and/or the reaction pressure is 1.0-8.0MPa; and/or the reaction temperature is 240-370 ℃; and/or the volume space velocity of the synthesis gas is 600-3000 hours -1 。
CN202110668294.5A 2021-06-16 2021-06-16 Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof Active CN115475637B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110668294.5A CN115475637B (en) 2021-06-16 2021-06-16 Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110668294.5A CN115475637B (en) 2021-06-16 2021-06-16 Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115475637A CN115475637A (en) 2022-12-16
CN115475637B true CN115475637B (en) 2024-01-30

Family

ID=84418887

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110668294.5A Active CN115475637B (en) 2021-06-16 2021-06-16 Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115475637B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103394354A (en) * 2013-08-22 2013-11-20 神华集团有限责任公司 Catalyst loaded on carbon sphere and preparation method of catalyst
CN103933989A (en) * 2013-01-23 2014-07-23 中国石油化工股份有限公司 Catalyst for synthesis of low carbon olefins and its preparation method
CN105195189A (en) * 2015-10-29 2015-12-30 江南大学 Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst
CN106000404A (en) * 2016-05-24 2016-10-12 江南大学 Preparation and application of carbon modified silicon dioxide carrier loaded iron-based catalyst for Fischer-Tropsch synthesis
WO2017173791A1 (en) * 2016-04-06 2017-10-12 中国科学院上海高等研究院 Cobalt carbide-based catalyst for direct preparation of olefin form synthesis gas, preparation method therefor and application thereof
CN107413362A (en) * 2017-08-10 2017-12-01 中南民族大学 A kind of fischer-tropsch synthesis process of super-active
CN107754793A (en) * 2017-11-23 2018-03-06 中科合成油技术有限公司 Fischer-tropsch synthetic catalyst of porous carbon load and its preparation method and application
CN110124729A (en) * 2019-06-13 2019-08-16 国家能源投资集团有限责任公司 A kind of coated catalyst and preparation method thereof for syrup state bed Fischer Tropsch synthesis

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933989A (en) * 2013-01-23 2014-07-23 中国石油化工股份有限公司 Catalyst for synthesis of low carbon olefins and its preparation method
CN103394354A (en) * 2013-08-22 2013-11-20 神华集团有限责任公司 Catalyst loaded on carbon sphere and preparation method of catalyst
CN105195189A (en) * 2015-10-29 2015-12-30 江南大学 Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst
WO2017173791A1 (en) * 2016-04-06 2017-10-12 中国科学院上海高等研究院 Cobalt carbide-based catalyst for direct preparation of olefin form synthesis gas, preparation method therefor and application thereof
CN106000404A (en) * 2016-05-24 2016-10-12 江南大学 Preparation and application of carbon modified silicon dioxide carrier loaded iron-based catalyst for Fischer-Tropsch synthesis
CN107413362A (en) * 2017-08-10 2017-12-01 中南民族大学 A kind of fischer-tropsch synthesis process of super-active
CN107754793A (en) * 2017-11-23 2018-03-06 中科合成油技术有限公司 Fischer-tropsch synthetic catalyst of porous carbon load and its preparation method and application
CN110124729A (en) * 2019-06-13 2019-08-16 国家能源投资集团有限责任公司 A kind of coated catalyst and preparation method thereof for syrup state bed Fischer Tropsch synthesis

Also Published As

Publication number Publication date
CN115475637A (en) 2022-12-16

Similar Documents

Publication Publication Date Title
CN111889132B (en) Metal oxide-molecular sieve catalyst, and preparation method and application thereof
CN114570360A (en) Ru-based catalyst and preparation method and application thereof
CN111229235A (en) NiO/MgAl2O4Catalyst, preparation method and application thereof
KR102035714B1 (en) Nickel catalysts for reforming hydrocarbons
WO2022166084A1 (en) Preparation method for and use of solvent coordination metal catalyst
CN111992213B (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN110787789A (en) Preparation and application of catalyst for preparing methanol by carbon dioxide hydrogenation
CN109675597A (en) A kind of preparation method of porous silicon carbide cobalt
CN111097429A (en) Catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof
KR20210000309A (en) Loaded catalyst in which an active metal is dispersed on an atomic scale in a carrier, and a method for producing and using the same
CN112403475B (en) Preparation method of catalyst for preparing synthesis gas by reforming carbon dioxide
CN115475637B (en) Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof
CN116474780A (en) For direct CO 2 Catalyst for preparing ethanol by hydrogenation, and preparation method and application thereof
CN114984952B (en) Carbon-coated copper material and preparation method and application thereof
CN114308061B (en) NiAu bimetallic alloy nano-catalyst and synthesis and application thereof
CN106391073A (en) Cobalt-based catalyst for directly preparing olefin from synthesis gas, and preparation method and application thereof
CN114308093B (en) High-load nickel-based carbide catalyst and preparation method and application thereof
CN115845885A (en) CdS/WC 1-x @ C composite photocatalyst and preparation method and application thereof
CN115228479A (en) Alkali metal modified NiSn material and preparation method and application thereof
CN115957786A (en) Nano core-shell cobalt-based catalyst and preparation and application thereof
CN114452990A (en) Method for preparing transition metal carbide and composite catalyst
CN113731422A (en) Preparation method of slurry bed methane synthesis catalyst
CN113926451A (en) Application of catalyst in catalyzing carbon dioxide hydrogenation reaction
CN116510732A (en) Alloy carbide catalyst, preparation method and application thereof
CN114620686B (en) Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant