CN117123225A - Iron-based catalyst for efficiently synthesizing carbonyl sulfide and preparation method thereof - Google Patents
Iron-based catalyst for efficiently synthesizing carbonyl sulfide and preparation method thereof Download PDFInfo
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 5
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical group O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 9
- 150000001728 carbonyl compounds Chemical class 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- -1 carbonyl thioester Chemical class 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- HQPMOXUTKURVDV-UHFFFAOYSA-L iron(2+);sulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O HQPMOXUTKURVDV-UHFFFAOYSA-L 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
- C01B32/77—Carbon oxysulfide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an iron-based catalyst for efficiently synthesizing carbonyl sulfide and a preparation method thereof. During calcination, the organic molecules in the precursor decompose at high temperature and are discharged to the environment in the form of gas, promoting the catalyst to form a pore structure. The method has simple synthesis conditions, rapid reaction and short time consumption, and the obtained catalyst has the carbonyl sulfide conversion rate of up to 100 percent at 450 ℃ and is suitable for the efficient production of carbonyl sulfide gas.
Description
Technical Field
The invention belongs to the field of inorganic material preparation, and particularly relates to an iron-based catalyst for efficiently synthesizing carbonyl sulfide and a preparation method thereof.
Background
Carbonyl sulfide can be used in the carbonylation reaction. The carbonylation reaction is a reaction for converting a compound such as an alcohol, acid, aldehyde, or ketone into a carbonyl compound such as an ester, acid anhydride, or amide. The carbonyl sulfide can be used as a catalyst for carbonylation reaction to promote the reaction. The carbonyl sulfide catalyzed carbonylation reaction has the advantages of mild reaction condition, high reaction speed, high yield and the like.
Carbonyl sulfide can be used for carbonyl addition reactions. Carbonyl addition reactions are reactions in which carbonyl compounds are reacted with nucleophiles (e.g., alcohols, amines, thiols, etc.) to form new compounds. The carbonyl sulfide can be used as a reagent for carbonyl addition reaction and reacts with a nucleophilic reagent to generate compounds such as carbonyl sulfide, thioester and the like. The carbonyl thioester and the thioester have higher reactivity and can further participate in other organic synthesis reactions.
Carbonyl sulfide can be used for carbonyl reduction reactions. The carbonyl reduction reaction is a reaction for reducing a carbonyl compound such as ketone or aldehyde to a corresponding alcohol. The carbonyl sulfide can act as a reducing agent for the carbonyl reduction reaction to reduce the carbonyl compound to the corresponding alcohol. The reduction reaction of carbonyl sulfide has the advantages of mild reaction conditions, high reduction efficiency and the like.
Carbonyl sulfide can also be used in carbonyl activation reactions. Carbonyl activation is a reaction that converts a carbonyl compound to a reactive intermediate. Carbonyl sulfide can be used as a reagent for carbonyl activation to convert carbonyl compounds to thiocarbonyl compounds. The thiocarbonyl compound has higher reactivity and can further participate in other organic synthesis reactions.
Moreover, in recent years, the electronic grade carbonyl sulfide special gas is widely applied to the fields of circuit fine etching and the like in the semiconductor production process, and is an important auxiliary raw material gas in the semiconductor production process of integrated circuits, chip manufacturing and the like.
However, in the conventional dry production process of carbonyl sulfide, the reaction temperature is high, and many side reactions are likely to occur, so that the purity of the finally obtained carbonyl sulfide gas is low.
Disclosure of Invention
The invention aims to provide a novel synthesis method of an iron-based catalyst, which has a carbonyl sulfide conversion rate of up to 100% at 450 ℃, is suitable for efficiently producing carbonyl sulfide gas, and can solve the problem of low carbonyl sulfide productivity at present.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the iron-based catalyst for efficiently synthesizing carbonyl sulfide comprises the steps of adding inorganic ferric salt, inorganic nickel salt, a template agent and urea into a polytetrafluoroethylene lining reaction kettle, stirring and mixing, then dropwise adding alkaline liquid to adjust the pH value, continuously stirring uniformly, then transferring into an oven for hydrothermal reaction, filtering a reaction product, and calcining to obtain the iron-based catalyst.
Further, the inorganic ferric salt is ferric sulfate pentahydrate, ferric nitrate nonahydrate or ferric chloride hexahydrate.
Further, the inorganic nickel salt is nickel sulfate hexahydrate, nickel nitrate hexahydrate or nickel chloride hexahydrate.
Further, the template is cetyl trimethylammonium bromide (CTAB).
Further, the mole percent ratio of the inorganic iron salt to the inorganic nickel salt used is 100:0-80:20.
Further, 0-2 g of template agent and 0-1 g of urea are used per 10 mmol according to the total mol of inorganic ferric salt and inorganic nickel salt.
Further, the alkaline liquid is ammonia water or NaOH solution.
Further, the pH value is adjusted to 8-11.
Further, the temperature of the hydrothermal reaction is 80-180 ℃ and the time is 6-24 hours.
Further, the calcination temperature is 400-700 ℃ and the calcination time is 1-10 h.
The obtained iron-based catalyst can be used for efficiently synthesizing carbonyl sulfide, and specifically, carbon monoxide and elemental sulfur steam are used as raw material gases, and the carbonyl sulfide is synthesized by catalyzing through the iron-based catalyst.
Further, the flow rates of the two raw material gases are 50 mL/min, and the reaction temperature is 450-600 ℃.
The invention has the remarkable advantages that:
(1) According to the invention, a hydrothermal synthesis method is used, CTAB and urea are added into a system as a template agent and a pore-forming agent, so that rich mesopores are formed; the added alkali can be used for adjusting the pH value to control the interaction type between the metal species and the template agent, thereby controlling the structural properties (such as porous structure, crystalline phase, morphology and the like) of the product.
(2) The method has simple synthesis conditions, rapid reaction and short time consumption.
Drawings
FIG. 1 is XRD spectra of iron-based catalysts prepared in examples 1 to 4 and comparative examples;
FIG. 2 is N of the iron-based catalysts prepared in examples 1 to 4 and comparative example 2 An adsorption and desorption graph (A) and a pore diameter distribution graph (B);
fig. 3 is an SEM image of the iron-based catalyst prepared in example 3.
Detailed Description
The iron-based catalyst for efficiently synthesizing carbonyl sulfide is prepared by weighing inorganic iron salt and inorganic nickel salt according to the mol percentage ratio of 100:0-80:20, weighing 0-2 g of template agent and 0-1 g of urea per 10 mmol of total metal salt, adding the template agent and urea into a polytetrafluoroethylene lining reaction kettle, stirring and mixing, then dripping alkaline liquid to adjust the pH value to 8-11, continuously stirring uniformly, transferring to an oven, carrying out hydrothermal reaction at 80-180 ℃ for 6-24 h, filtering a reaction product, and calcining at 400-700 ℃ for 1-10 h to obtain the nickel-doped ferric oxide catalyst.
Wherein the inorganic ferric salt is ferric sulfate pentahydrate, ferric nitrate nonahydrate or ferric chloride hexahydrate. The inorganic nickel salt is nickel sulfate hexahydrate, nickel nitrate hexahydrate or nickel chloride hexahydrate. The template agent is Cetyl Trimethyl Ammonium Bromide (CTAB). The alkaline liquid is ammonia water or NaOH solution.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1:
ferric nitrate nonahydrate 3.636 g (9 mmol), nickel nitrate hexahydrate 0.291 g (1 mmol), CTAB 0.4 g and urea 0.1 g were weighed into 100 mL water, respectively. After being evenly mixed, the pH value is adjusted to 8 by ammonia water, stirring is continued, and then hydrothermal reaction is carried out at 100 ℃ for 24 h. After the reaction is finished and cooled to room temperature, the reaction product is filtered to be neutral to obtain an initial product, the initial product is calcined in a muffle furnace at 400 ℃ for 2 h, and after natural cooling, the 10% nickel-doped iron oxide catalyst for synthesizing carbonyl sulfide is obtained and is marked as a catalyst A.
Example 2:
iron sulfate pentahydrate 3.920 g (8 mmol), nickel sulfate hexahydrate 0.526 g (2 mmol), CTAB 1 g, urea 1 g were weighed separately into 100 mL water. After being uniformly mixed, the pH value is adjusted to 11 by ammonia water, stirring is continued, and then the hydrothermal reaction is carried out at 140 ℃ for 16 h. After the reaction is finished and cooled to room temperature, the reaction product is filtered to be neutral to obtain an initial product, the initial product is calcined in a muffle furnace at 600 ℃ for 6 h, and after natural cooling, the 20% nickel-doped iron oxide catalyst for synthesizing carbonyl sulfide is obtained and is marked as a catalyst B.
Example 3:
iron sulfate pentahydrate 4.655 g (9.5 mmol), nickel sulfate hexahydrate 0.013 g (0.5 mmol), CTAB 2 g, urea 0.5 g were weighed separately into 100 mL water. After being uniformly mixed, the pH value is adjusted to 10 by ammonia water, stirring is continued, and then the hydrothermal reaction is carried out at 180 ℃ for 12 h. After the reaction is finished and cooled to room temperature, the reaction product is filtered to be neutral to obtain an initial product, the initial product is calcined in a muffle furnace at 700 ℃ for 4h, and after the initial product is naturally cooled, the 5% nickel-doped iron oxide catalyst for synthesizing carbonyl sulfide is obtained and is marked as a catalyst C.
Example 4:
iron chloride hexahydrate 2.433 g (9.9 mmol), nickel chloride hexahydrate 0.024 g (0.1 mmol), CTAB 1.5 g, urea 0.1 g were weighed separately into 100 mL water. After being evenly mixed, the pH value is adjusted to 9 by ammonia water, stirring is continued, and then the hydrothermal reaction is carried out at 180 ℃ for 12 h. After the reaction is finished and cooled to room temperature, the reaction product is filtered to be neutral to obtain an initial product, the initial product is calcined in a muffle furnace at 550 ℃ for 8 h, and after the initial product is naturally cooled, the 1% nickel-doped iron oxide catalyst for synthesizing carbonyl sulfide is obtained and is marked as a catalyst D.
Comparative example:
ferric nitrate nonahydrate 4.04 g (10 mmol), CTAB 1 g and urea 0.1 g were weighed separately and added to 100 mL water. After being evenly mixed, the pH value is adjusted to 8 by ammonia water, stirring is continued, and then the hydrothermal reaction is carried out at 80 ℃ for 6 h. After the reaction is cooled to room temperature, carrying out suction filtration to neutrality to obtain an initial product, calcining the initial product in a muffle furnace at 600 ℃ for 5 h, and naturally cooling to obtain an iron oxide catalyst, which is denoted as a catalyst E.
The resulting catalyst was analyzed and tested accordingly:
fig. 1 is an XRD spectrum of the iron-based catalyst prepared in examples 1 to 4 and comparative example. As can be seen from the graph, characteristic derivative peaks of 24.2 degrees, 33.2 degrees, 35.7 degrees, 40.9 degrees, 49.5 degrees, 54.1 degrees, 62.5 degrees and 64.0 degrees of ferric oxide appear in all five samples, which indicate that doping of nickel does not influence alpha-Fe 2 O 3 Is a crystal phase structure of (a).
FIG. 2 is N at liquid nitrogen temperature for the catalyst prepared in example 3 2 A physical adsorption/desorption isotherm (A) and a pore diameter distribution diagram (B) thereof. It can be seen from the figure that catalyst C contains not only a large number of mesopores but also a certain number of micropores.
Fig. 3 is an SEM image of the iron-based catalyst prepared in example 3. The figure shows that the synthesized nickel-doped ferric oxide is formed by stacking nano small particles, and the particle size is uniform, so that the adsorption catalysis of gas in the reaction process is facilitated.
The activity of the catalyst is expressed in terms of carbonyl sulfide conversion and carbonyl sulfide selectivity, and the carbonyl sulfide concentration was tested using on-line chromatography. The test conditions are as follows: the activity test of synthesizing carbonyl sulfide is carried out in a fixed bed quartz reactor, the catalyst loading is 0.2: 0.2 g, the height is about 1: 1 cm, the granularity is 40-60 meshes, the reaction temperature is 450-600 ℃, sampling measurement is carried out after the reaction is carried out for 1h at each reaction temperature, the heating rate is 3 ℃/min, and the interval between the test temperature points is 20 ℃. The reaction tube is a quartz tube with an inner diameter of 5 mm and a flow rate of the raw material gas (carbon monoxide and elemental sulfur vapor) of 50 mL/min. The test results are shown in tables 1 and 2, respectively.
TABLE 1 carbonyl Sulfur conversion of different catalysts
TABLE 2 carbonyl sulfide selectivity for different catalysts
As can be seen from Table 1, the activity of catalyst C was significantly higher than A, B, D in catalysts with different nickel doping levels, which had achieved 100% carbonyl sulfide conversion at 450℃while the other catalysts had 100% conversion at 540℃or higher, and undoped catalyst E had not achieved 100% conversion throughout the test temperature range.
As can be seen from Table 2, the selectivity of catalyst A, B, C, D was 100% at 450℃and the conversion of catalyst C alone was 100% in this case, as can be seen from Table 1, indicating that the purity of the gaseous product of catalyst C alone was 100%. While all catalysts show a decrease in selectivity as the temperature continues to rise.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The preparation method of the iron-based catalyst for efficiently synthesizing carbonyl sulfide is characterized by mixing inorganic ferric salt, inorganic nickel salt, a template agent and urea under stirring, then dropwise adding alkaline liquid to adjust the pH value, continuously stirring uniformly, then carrying out hydrothermal reaction, filtering a reaction product, and calcining to obtain the iron-based catalyst.
2. The method for preparing an iron-based catalyst according to claim 1, wherein: the mole percentage ratio of the inorganic ferric salt to the inorganic nickel salt is 100:0-80:20, and 0-2 g of template agent and 0-1 g of urea are used per 10 mmol according to the total mole of the inorganic ferric salt and the inorganic nickel salt.
3. The method for producing an iron-based catalyst according to claim 1 or 2, characterized in that: the inorganic ferric salt is ferric sulfate pentahydrate, ferric nitrate nonahydrate or ferric chloride hexahydrate; the inorganic nickel salt is nickel sulfate hexahydrate, nickel nitrate hexahydrate or nickel chloride hexahydrate; the template agent is CTAB.
4. The method for preparing an iron-based catalyst according to claim 1, wherein: the alkaline liquid is ammonia water or NaOH solution.
5. The method for preparing an iron-based catalyst according to claim 1, wherein: the pH value is adjusted to 8-11.
6. The method for preparing an iron-based catalyst according to claim 1, wherein: the temperature of the hydrothermal reaction is 80-180 ℃ and the time is 6-24 hours.
7. The method for preparing an iron-based catalyst according to claim 1, wherein: the calcination temperature is 400-700 ℃ and the calcination time is 1-10 h.
8. An iron-based catalyst prepared by the method of any one of claims 1-7.
9. Use of the iron-based catalyst according to claim 8 for the efficient synthesis of carbonyl sulfide, characterized in that: carbon monoxide and elemental sulfur steam are used as raw material gases, and are catalyzed by the iron-based catalyst to realize the synthesis of carbonyl sulfide.
10. The use according to claim 9, characterized in that: the flow rates of the two raw material gases are 50 mL/min, and the reaction temperature is 450-600 ℃.
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