CN113908859B - Mesoporous iron disulfide catalyst and preparation method and application thereof - Google Patents
Mesoporous iron disulfide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910000339 iron disulfide Inorganic materials 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- -1 iron ions Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 239000012053 oil suspension Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 150000002505 iron Chemical class 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/613—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/06—Sulfides
Abstract
The invention discloses a mesoporous iron disulfide catalyst and a preparation method and application thereof, belonging to the technical field of petroleum processing. Adding an alkali solution into an inorganic iron salt solution to completely precipitate iron ions, washing and drying the precipitate, uniformly mixing the precipitate with sulfur powder, and roasting the mixture in a nitrogen atmosphere to obtain mesoporous FeS 2 . The invention has simple synthesis process, short synthesis period and low cost. The FeS thus obtained 2 Has large specific surface area, mesoporous structure and initial H at the reaction temperature of 430 DEG C 2 Under the pressure of 13.0 MPa, the hydrocracking reaction result of the residual oil suspension bed is as follows: the conversion rate of residual oil is 85% at most, and the yield of naphtha and middle distillate oil can reach 55 wt%. The economic benefit is obvious, and the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of petroleum processing, and particularly relates to a mesoporous iron disulfide catalyst, and a preparation method and application thereof.
Background
Petroleum is an important energy pillar for social development, and not only occupies a great proportion in an energy structure, but also plays an important role in promoting economic development and social progress. However, the crude oil has a serious tendency of heaviness and deterioration, and the efficient utilization of the inferior heavy oil is the key to solve the energy problem. Currently, among the numerous residual oil hydrocracking technologies, the suspension bed hydrocracking technology is favored. The catalysts used in this technique include homogeneous catalysts and heterogeneous catalysts, including supported and solid powder catalysts. The supported catalyst is prepared by loading transition metal on alumina, molecular sieve and the like. The use of transition metals Mo, co and Ni greatly increases the production cost of the catalyst, and the catalyst is limited in the hydrocracking reaction of the suspension bed.
The natural iron ore has wide source, low price and certain hydrogenation reaction performance, and therefore, the natural iron ore is used as a catalyst for the hydrocracking reaction of the suspension bed. Because the content of Fe in natural minerals is low, the composition structure is uncertain, and the reaction activity of the suspension hydrocracking reaction of heavy oil is low. The design and preparation of the high-purity Fe-based catalyst are effective means for solving the problem of low hydrocracking reaction activity of the natural Fe ore catalyst. At present, all catalysts used for the hydrocracking reaction of the heavy oil suspension bed are metal oxidation state catalysts, however, the hydrogenation active site is a metal sulfide in the hydrocracking reaction, and for this reason, the catalyst needs to be sulfurized to obtain the metal sulfide before the reaction evaluation. Based on the analysis, the application proposes to design and prepare the sulfide of Fe for the residual oil suspension bed hydrocracking catalyst, so as to simplify the reaction evaluation process, reduce the energy consumption and save the oil product production cost.
The preparation of Fe sulfide has been reported, feS 2 The synthesis method of (2) is mainly hydrothermal and solvothermal synthesis based on high-temperature reaction. The high group topic group utilizes a method of roasting FeS in an oxygen-free environment after mixing iron oxyhydroxide and sulfur powder 2 (CN 105883935A); ma Huaijun subject group adopts hydrothermal synthesis method to prepare nano amphiphilic iron sulfide catalyst, which shows better hydrogenation deasphalting, hydrodesulfurization, hydrodenitrogenation and aromatic hydrogenation reaction performances in heavy oil suspension bed hydrogenation reaction (CN 106799240A); any Xiang Kun group uses a catalyst prepared by using iron sulfide ore to load metal molybdenum for a coal tar hydrocracking reaction, and the hydrogenation effect is still good (CN 103877999A). Jiang et al ground iron salts and sulfur sources and then calcined in an inert gas atmosphere to produce FeS 2 (US 15862606); the Schimek utilizes the reaction of ferric oxide, hydrogen sulfide and elemental sulfur at the temperature higher than the melting point of the elemental sulfur to obtain FeS 2 (CA 2700185C). FeCl is added 2 Mixing sodium hydroxide and sulfur powder, and reacting under certain conditions to obtain FeS 2 (EP 2955775A 1); leonard et al forebody sulfur and ironDirectly mixing the mixture to prepare FeS 2 (US 10457566B 2); matthew method for producing FeCl 2 Mixing the octadecylamine, degassing and sulfur, and reacting under certain conditions to finally obtain FeS 2 (US 9862617B 2). FeS prepared by the method 2 The catalyst has no smooth mesoporous structure and is difficult to satisfy the hydrocracking reaction of the heavy oil macromolecule suspension bed.
Disclosure of Invention
The invention aims to provide a mesoporous iron disulfide catalyst suitable for poor-quality residual oil suspension bed hydrocracking reaction, a preparation method thereof and prepared FeS 2 The catalyst has a mesoporous structure and a large specific surface area, and has the advantages of cheap raw materials, short synthesis period, greenness and no pollution. The catalyst shows good effect in the poor-quality residual oil suspension bed hydrocracking reaction with less dosage, and has good commercial and industrial application value.
In order to realize the purpose, the invention adopts the following technical scheme:
with FeCl 3 ·6H 2 O、Fe 2 (SO 4 ) 3 ·xH 2 O is an inorganic iron source, sublimed sulfur is used as a vulcanizing agent, and the mixture is roasted under the condition of isolating oxygen to prepare iron sulfide.
The preparation steps are as follows:
adding inorganic ferric salt into deionized water to obtain an inorganic ferric salt solution, and carrying out water bath treatment on the inorganic ferric salt solution;
adding an alkaline solution into the inorganic iron salt solution obtained in the step (1), and stopping adding the alkaline solution after iron ions are completely precipitated;
step (3), washing and drying the precipitate generated in the step (2) to obtain solid powder, and grinding and mixing the solid powder and sulfur powder until the solid powder and the sulfur powder are uniform;
and (4) drying and roasting the mixture obtained in the step (3) to obtain the iron sulfide.
The inorganic ferric salt used in the step (1) is FeCl 3 ·6H 2 O or Fe 2 (SO 4 ) 3 ·xH 2 O, the purity of the iron salt solution is higher than the industrial purity, and the concentration of the iron salt solution is 2-8 mol/L.
The water bath heating temperature in the step (1) is 50-90 ℃, the rotating speed is 400-800 r/min, and the reaction time is 0.5-5 h.
In the step (2), the alkaline solution is ammonia water or NaOH solution, and the concentration of the alkaline solution is 2-7 mol/L; the pH of the solution is 7.0-10.0.
The particle size of the mixture ground in the step (3) is less than 40 meshes; the drying temperature is 80-180 ℃; the mass ratio of the solid powder to the sulfur powder is 100.
The drying process in the step (4) is vacuum drying, and the drying temperature is 50-80 ℃; calcination of the mixture to N 2 The roasting is carried out in the atmosphere, the roasting temperature is 300-700 ℃, and the roasting time is 2-10 h.
The FeS thus obtained 2 Is a mesoporous material, has an average pore diameter of 5.2-15.9 nm, a pore volume of 0.10-0.35 cm and a specific surface area of 25-120 m/g.
The invention has the beneficial effects that: the invention has simple synthesis process, short synthesis period and low cost. The FeS thus obtained 2 Has large specific surface area, mesoporous structure and initial H at the reaction temperature of 430 DEG C 2 Under the pressure of 13.0 MPa, the hydrocracking reaction result of the residual oil suspension bed is as follows: the conversion rate of the residual oil is 85% at most, and the yield of naphtha and middle distillate oil can reach 55 wt%. The economic benefit is obvious, and the application prospect is wide.
Drawings
FIG. 1 is FeS prepared according to the present invention 2 Wide angle XRD pattern of the catalyst;
FIG. 2 is FeS prepared according to the present invention 2 The nitrogen of the catalyst is absorbed and removed from the attached figure;
FIG. 3 is FeS prepared according to the present invention 2 Pore size distribution of the catalyst.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
In order to avoid repetition, the raw materials used are uniformly described as follows, and are not described in the examples. The purity of the iron salt is more than industrial purity. The purities of the NaOH and the ammonia water are more than industrial purities.
Example 1
27.05 gFeCl 3 ·6H 2 O is added into 39.2 ml deionized water to prepare 2 mol/L FeCl 3 Stirring the solution in water bath at 80 ℃ for 1 h; the prepared 6 mol/L NaOH solution is dropwise added into FeCl 3 And (4) stopping dripping the NaOH solution when the pH value of the solution is more than 11.2. The prepared reddish brown precipitate is washed by deionized water for several times, dried at 95 ℃ for 6 h to obtain a solid substance, ground and screened to obtain particles with the particle size of less than 20 meshes, then uniformly mixed with sulfur powder, and roasted at 500 ℃ in a nitrogen atmosphere for 6 h to obtain the required sample.
Preparation of FeS 2 Has a specific surface area of 29.4 m/g, a pore volume of 0.100 cm large face/g and an average pore diameter of 14.4 nm. The evaluation result of the residual oil suspension bed hydrocracking reaction of the catalyst is as follows: at a temperature of 430 ℃ with initial H 2 2 h reacted at 13 MPa with a bottoms conversion of 76.3%, naphtha and middle distillate yields of about 58.7 wt%, and coke yield of 4.6 wt%.
Example 2
27.05 gFeCl 3 ·6H 2 Adding O into the deionized water of 39.2 ml to prepare FeCl of 2 mol/L 3 Stirring the solution in water bath at 80 ℃ for 1 h; the prepared 6 mol/L NaOH solution is dropwise added into FeCl 3 And (4) stopping dripping the NaOH solution when the pH value of the solution is more than 9.8. The prepared reddish brown precipitate is washed by deionized water for several times, dried at 95 ℃ for 6 h to obtain a solid substance, ground and screened to obtain particles with the particle size of less than 20 meshes, then uniformly mixed with sulfur powder, and roasted at 500 ℃ in a nitrogen atmosphere for 6 h to obtain the required sample.
Preparation of FeS 2 Has a specific surface area of 28.1 m/g, a pore volume of 0.120 cm large face/g and an average pore diameter of 16.0 nm. The evaluation result of the residual oil suspension bed hydrocracking reaction of the catalyst is as follows: at a temperature of 430 ℃ with initial H 2 2 h reacted at 13 MPa, resid conversion 79.0%, naphtha and middle distillate yield of about 57.6 wt%, coke yield of 3.5 wt%.
Example 3
27.05 gFeCl 3 ·6H 2 O is added into 39.2 ml deionized water to prepare 2 mol/L FeCl 3 Stirring the solution in water bath at 80 ℃ for 1 h; adding ammonia solution dropwise to FeCl 3 And (4) stopping dropwise adding the ammonia water solution into the solution until the pH value of the solution is 8.9. The prepared reddish brown precipitate is washed by deionized water for several times, poured into a reactor, added, mixed with sulfur powder and a small amount of water, stirred for 6 hours at room temperature, dried in vacuum at 60 ℃ for 48 h, and roasted at 500 ℃ in nitrogen atmosphere for 6 h to prepare the required sample.
Preparation of FeS 2 Has a specific surface area of 30.5 m/g, a pore volume of 0.110 cm large face/g and an average pore diameter of 15.3 nm. The evaluation result of the residual oil suspension bed hydrocracking reaction of the catalyst is as follows: at a temperature of 430 ℃ with initial H 2 2 h reacted at 13 MPa with a bottoms conversion of 83.5%, naphtha and middle distillate yield of about 59.5 wt%, and coke yield of 1.3 wt%.
Example 4
27.05 gFeCl 3 ·6H 2 O is added into 39.2 ml deionized water to prepare 2 mol/L FeCl 3 Stirring the solution in water bath at 80 ℃ for 1 h; the prepared 6 mol/L NaOH solution is dropwise added into FeCl 3 And (4) stopping dripping the NaOH solution when the pH value of the solution is more than 11.2. Washing the prepared reddish brown precipitate with deionized water for several times, drying at 95 deg.C for 6H to obtain solid matter, grinding, sieving to obtain particles with particle size less than 20 mesh, mixing with sulfur powder, and mixing at 500 deg.C and 2% H 2 S and 98% N 2 Roasting 6 h under the atmosphere condition to prepare the required sample.
Preparation of FeS 2 Has a specific surface area of 60.5 m/g, the pore volume was 0.220 cm and average pore diameter was 9.3 nm. The evaluation result of the residual oil suspension bed hydrocracking reaction of the catalyst is as follows: at a temperature of 430 ℃ with initial H 2 2 h reacted at 13 MPa, the bottoms conversion was 85.7%, the yield of naphtha and middle distillate was about 59.2 wt%, and the coke yield was 1.6 wt%.
Example 5
27.05 gFeCl 3 ·6H 2 O is added into 39.2 ml deionized water to prepare 2 mol/L FeCl 3 Stirring the solution in water bath at 80 ℃ for 1 h; adding ammonia solution dropwise to FeCl 3 And (4) stopping dropwise adding the ammonia water solution into the solution until the pH value of the solution is 8.9. The prepared reddish brown precipitate is washed by deionized water for several times, poured into a reactor, added, mixed with sulfur powder and a small amount of water, stirred for 6 hours at room temperature, dried in vacuum at 60 ℃ for 48 h, and roasted at 500 ℃ in nitrogen atmosphere for 6 h to prepare the required sample.
Preparation of FeS 2 Has a specific surface area of 46.9 m/g, the pore volume was 0.110 cm and average pore diameter was 11.6 nm. The evaluation result of the residual oil suspension bed hydrocracking reaction of the catalyst is as follows: at a temperature of 430 ℃ with initial H 2 2 h reacted at 13 MPa, the bottoms conversion was 80.2%, the yield of naphtha and middle distillate was about 57.3 wt%, and the coke yield was 2.8 wt%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. The application of the mesoporous iron disulfide catalyst in the hydrocracking reaction of the suspension bed is characterized in that: the preparation method of the mesoporous iron disulfide catalyst comprises the following steps:
(1) Adding inorganic ferric salt into deionized water, heating and stirring;
(2) Adding alkaline solution to completely precipitate iron ions;
(3) Washing and drying the precipitate to obtain solid powder;
(4) Mixing the solid powder with sulfur powder, and uniformly grinding;
(5) And (3) roasting the mixture obtained in the step (4) in a nitrogen atmosphere to obtain the mesoporous iron disulfide, wherein the average pore diameter of the mesoporous iron disulfide is 5.2-15.9 nm, the pore volume of the mesoporous iron disulfide is 0.10-0.35 cm and the specific surface area of the mesoporous iron disulfide is 25-120 m/g.
2. Use according to claim 1, characterized in that: in the step (1), the inorganic ferric salt is ferric chloride or ferric sulfate, and the concentration of the obtained ferric salt solution is 2-8 mol/L; the heating temperature is 30-90 ℃, and the stirring speed is 400-800 r/min.
3. Use according to claim 1, characterized in that: in the step (2), the alkaline solution is ammonia water or NaOH solution, and the concentration of the alkaline solution is 2-7 mol/L; the pH value of the system is controlled to be 7.0-10.0.
4. Use according to claim 1, characterized in that: the drying temperature in the step (3) is 80-180 ℃.
5. Use according to claim 1, characterized in that: in the step (4), the mass ratio of the solid powder to the sulfur powder is 100.
6. Use according to claim 1, characterized in that: in the step (5), the roasting temperature is 300-700 ℃, and the roasting time is 2-10 h.
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| CN101119934A (en) * | 2005-02-16 | 2008-02-06 | 独立行政法人科学技术振兴机构 | Method for producing iron oxyhydroxide and adsorbing material comprising iron oxyhydroxide |
| CN106799240B (en) * | 2015-11-26 | 2019-08-02 | 中国科学院大连化学物理研究所 | A kind of surface amphiphilic nano vulcanization iron catalyst and the preparation method and application thereof |
| CN105883935B (en) * | 2016-04-11 | 2018-01-16 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of ferrous disulfide |
| CN107162065B (en) * | 2017-05-10 | 2018-11-20 | 山东科技大学 | A kind of coal liquefaction FeS2The preparation method of nano tube catalyst |
| CN108675357A (en) * | 2018-06-28 | 2018-10-19 | 福州大学 | A kind of preparation method and applications of inorganic hole transporter ferrous disulfide |
| JP7098043B2 (en) * | 2018-09-18 | 2022-07-08 | エルジー エナジー ソリューション リミテッド | A method for producing iron sulfide, a positive electrode for a lithium secondary battery containing iron sulfide produced from the method, and a lithium secondary battery provided with the positive electrode. |
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