WO2022119191A1 - 담체 기공이 조절된 탈수소화 촉매 - Google Patents
담체 기공이 조절된 탈수소화 촉매 Download PDFInfo
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- WO2022119191A1 WO2022119191A1 PCT/KR2021/016938 KR2021016938W WO2022119191A1 WO 2022119191 A1 WO2022119191 A1 WO 2022119191A1 KR 2021016938 W KR2021016938 W KR 2021016938W WO 2022119191 A1 WO2022119191 A1 WO 2022119191A1
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- Prior art keywords
- catalyst
- platinum
- carrier
- alumina
- tin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 25
- 239000011148 porous material Substances 0.000 title claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 13
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 13
- 210000003278 egg shell Anatomy 0.000 claims abstract description 13
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 4
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 239000001294 propane Substances 0.000 abstract description 7
- -1 propane and butane Chemical class 0.000 abstract description 4
- 239000001273 butane Substances 0.000 abstract description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 229910052718 tin Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- B01J35/397—
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
- C07C5/324—Catalytic processes with metals
- C07C5/325—Catalytic processes with metals of the platinum group
-
- 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
Definitions
- the present invention relates to a dehydrogenation catalyst and a method for preparing the same, and more particularly, a spherical platinum-based catalyst containing tin and potassium components used for the dehydrogenation catalysis of light hydrocarbons in the C3 to C5 range, such as propane and butane.
- the catalyst carrier has a pore size and a surface area controlled by heat treatment, and relates to a dehydrogenation catalyst in which platinum and tin alloy components exist in egg-shell form only to a certain depth from the catalyst surface.
- the catalyst carrier is a mixture of gamma alumina and theta alumina, having a pore volume of 0.5 to 0.65 cc/g, the platinum dispersion of the catalyst is 30 to 50%, and the platinum average particle size is 3 nm to 5 nm to be.
- Light olefins are materials used for various commercial purposes, such as plastics, synthetic rubbers, pharmaceuticals, and raw materials for chemical products, and can be prepared by the following dehydrogenation of light hydrocarbons.
- Catalysts that promote the light hydrocarbon dehydrogenation reaction are mainly spherical shaped carriers with micropores such as alumina, zeolite, silica, and spinel-type metal aluminate. These materials are effective in coking resistance and product selectivity, but the reaction is poor As the amount of coke accumulated in the catalyst gradually increases as the process progresses, the micropores are clogged by the coke and the active metals present inside the pores are eventually deactivated without participating in the reaction. A carrier capable of reducing side reactions such as cracking and coke deposition structure is required.
- an alumina carrier in which the pore size can be controlled relatively easily only by heat treatment, is mainly applied.
- gamma alumina is vulnerable to coke deposition due to its small pore size, and side reactions proceed due to carrier acid sites. The disadvantage is that the conversion rate is low.
- the present inventors have studied the dehydrogenation catalyst carrier, and the mixed carrier of alpha-alumina and theta-alumina can suppress side reactions by removing acid sites through high-temperature heat treatment. and selectivity were found to be advantageous.
- the above object is to heat a porous alumina carrier to form a mixture of gamma alumina and theta alumina having an appropriate pore size and surface area, and platinum and tin alloy components are present only in an egg-shell form only to a certain depth from the catalyst surface by a dehydrogenation catalyst.
- the carrier of the catalyst according to the present invention has a pore volume of 0.5 to 0.65 cc/g, the platinum dispersion of the catalyst is 30 to 50%, and the platinum average particle size may be 3 nm to 5 nm .
- the platinum-tin alloy is distributed in an egg-shell form on a carrier with controlled pore size and surface area, and the dispersion of active metal is maximized, so that the conversion rate and selectivity are high even during long-term operation in the dehydrogenation process. can be kept high.
- the active metal egg-shell type catalyst according to the present invention is a porous alumina carrier, in particular, a mixture of alpha-alumina and theta-alumina is applied as a carrier, and platinum, tin, and potassium are impregnated in the carrier. It is distributed in an egg-shell structure to the depth, and potassium is uniformly distributed throughout the interior of the carrier.
- the catalyst refers to a spherical catalyst, in which active ingredients and/or sub-components are supported on a spherical support.
- the presence of the active ingredient and/or the active ingredient and the sub-generated tin component in the form of an egg-shell is a form that exists in a certain thickness from the catalyst surface toward the catalyst center, and in that it forms a thickness directly from the catalyst surface, these are on the catalyst surface. It is distinguished from the cyclic form in which no component is present.
- the active ingredient is mainly described with palladium, and tin and potassium ingredients are exemplified in the subsidy, but the present invention is not limited thereto, and metal ingredients having the same purpose and function understood by those skilled in the art can be easily applied in the present invention, of course. to be.
- the carrier of the catalyst implemented herein may preferably have a pore volume of 0.5 to 0.65 cc/g, the dispersion degree of platinum in the catalyst is 30 to 50%, and the average particle size of the platinum-tin alloy is 3 nm to 5 nm However, only examples having representative values within these numerical ranges are described as examples.
- the egg-shell type platinum catalyst having a specific structure according to the present invention can be schematically prepared through the following steps.
- the organic solvent for the above purpose is one or two solvents among methanol, ethanol, butanol, acetone, ethyl acetate, acenonitrile, ethylene glycol, tri-ethylene glycol, glycol ether, glycerol, sorbitol, xylitol, dialkyl ether, tetrahydrofuran It can be selected from, and can be used sequentially or as a mixed solution.
- Platinum-tin mixed solution is uniformly impregnated into a porous alumina carrier: To control pore size and pore volume, use a porous alumina carrier of alpha and theta crystallinity heat treated at 850-1100 degrees in a kiln. The prepared platinum-tin solution is impregnated into the heat-treated carrier by spray deposition. The heat treatment temperature is closely related to the crystalline phase and pore structure of the carrier, and when the heat treatment temperature is 850 degrees or less, the gamma phase is the main crystalline phase of alumina, and the pore size of the carrier is small, so the diffusion rate of the reactant in the carrier may be lowered.
- the heat treatment temperature is 1100 degrees or more, the crystal phase of alumina is predominantly alpha phase, and the pore size exists in a favorable state for the reaction, but the dispersion degree of active metals distributed in the alpha alumina phase in the process of supporting the active metal is high. Therefore, the heat treatment temperature is set to 850-1100 degrees to reform into a mixed state of alpha and theta alumina.
- the metal in the carrier After impregnation, the metal in the carrier is fixed by drying it in a dryer at 100-150 degrees or more for 12 hours or more, and then calcining in an air atmosphere in the range of 400-700 degrees.
- Alkali metal support and fixation Alkali metal is supported in order to suppress side reactions caused by acid sites remaining on the porous alumina support. Potassium is supported in the pores of the carrier by a spray deposition method, dried in a dryer at 100-150 degrees for 12 hours or more, and calcined in an air atmosphere in the range of 400-700 degrees to fix potassium in the carrier.
- the reduction process is performed using hydrogen gas within the range of 400-600 degrees to obtain the final catalyst.
- the metal oxidizing species may not be completely reduced, and when the temperature is higher than 600 degrees, aggregation and sintering of the metal particles may occur and the active point may be reduced.
- a carbon monoxide adsorption experiment was performed in order to confirm the degree of dispersion of the metal active material for the catalyst according to the present invention.
- the temperature is raised to 400 degrees with helium gas, and then moisture in the catalyst is removed through oxygen and hydrogen treatment and unreduced metal oxides are reduced.
- 7% carbon monoxide gas is injected and the amount of carbon monoxide gas adsorbed to the precious metal is analyzed. Assuming that carbon monoxide and platinum are adsorbed in a 1:1 ratio, the dispersion degree and particle size of platinum are finally calculated.
- paraffin, isoparaffin a hydrocarbon having a number of carbon atoms of 2 to 5, preferably 3 to 4, including alkyl aromatics
- the dehydrogenation reaction is carried out as a gas phase reaction under the conditions of 570° C., 0-2 atm, preferably 1.5 atm, and a Liquid Hourly Space Velocity (LHSV) of 1-40 h ⁇ 1 of paraffin hydrocarbons.
- LHSV Liquid Hourly Space Velocity
- a bead-type alumina carrier was used by heat treatment at 950 degrees. Chloroplatinic acid was used as a platinum precursor and tin chloride was used as a tin precursor, and 0.2wt% of tin chloride and 5% of the total solution were mixed with hydrochloric acid. Then, chloroplatinic acid corresponding to 0.4wt% of the total weight of the catalyst was added to prepare a platinum-tin solution, and then added to ethanol in an amount corresponding to the total pore volume of the carrier and dissolved. The platinum-tin solution was impregnated into the prepared alumina carrier by spray deposition. After drying the carrier on which the platinum-tin mixed solution was supported at 120° C.
- Example 1 a catalyst was prepared by a platinum-tin co-impregnation method.
- a comparative catalyst was prepared by sequentially impregnating platinum, tin, and potassium. Alumina heat-treated in the same manner as in Example 1 was used. Using chloroplatinic acid as a platinum precursor, a solution of 0.4wt% of platinum with respect to the total weight of the catalyst and 5wt% of hydrochloric acid of the total solution is diluted in deionized water corresponding to the total pore volume of the carrier and sprayed. It was impregnated in the carrier by the support method. The platinum-supported carrier was dried and heat-treated as in Example 1 to fix the active metal.
- a catalyst was prepared in the same manner as in Example 1, except that the bead-type alumina carrier was heat-treated at 850°C.
- a catalyst was prepared in the same manner as in Example 1, except that the bead-type alumina carrier was heat-treated at 1050°C.
- a catalyst was prepared in the same manner as in Example 1, except that the bead-type alumina carrier was heat-treated at 1100°C.
- Catalysts according to Examples and Comparative Examples were charged in a fixed-bed catalytic reactor to carry out propane dehydrogenation reaction.
- the composition of the reaction gas in the reactor has a volume ratio of hydrogen and propane of 0.61, and 95 ppm of the total gas is composed of H 2 S gas to prevent corrosion of the SUS reactor.
- propane dehydrogenation reaction proceeds while adding propane and hydrogen in the above constant ratio.
- the conversion rate and selectivity are calculated by analyzing the gas produced using gas chromatography.
- Table 1 summarizes the dispersion degree measurement results and propane dehydrogenation reaction results of platinum using carbon monoxide adsorption for catalysts according to Examples and Comparative Examples, and Table 2 summarizes changes in the surface area and pore structure of the heat-treated carrier did it 1 shows the change in conversion and selectivity over time.
- Example 1 prepared using a platinum-tin mixed solution had a higher platinum dispersion than Comparative Example 1 prepared through a sequential method.
- the alloy catalyst with high dispersion has high initial conversion and selectivity, showing high propylene yield. After all catalysts in the test have been activated for 10 hours, the propylene yield due to platinum sintering and carbon deposition decreases, but the initial dispersion value is For the high platinum-tin alloy catalyst, the yield reduction rate was low compared to the comparative catalyst prepared by sequential impregnation.
Abstract
Description
구분 | 활성금속 분포형태 | 담체 소성온도 (℃) |
분산도 (%) |
활성금속 평균 입자크기 (nm) |
전환율 (%) Ci/Cf |
선택도 (%) Si/Sf |
수율 (%) Yi/Yf |
수율 감소율 (%) |
실시예 1 | 에그-쉘 | 950 | 36.2 | 3.13 | 37.0/36.1 | 90.1/89.9 | 33.3/32.5 | 2.65 |
비교예 1 | 전체분포 | 950 | 21.2 | 5.34 | 36.2/34.5 | 90.0/89.6 | 32.6/30.9 | 5.12 |
비교예 2 | 에그-쉘 | 850 | 42 | 2.70 | 39.1/37.9 | 82.2/77.8 | 32.1/29.5 | 8.26 |
비교예 3 | 에그-쉘 | 1050 | 32.8 | 3.45 | 36.7/35.5 | 91.0/90.5 | 33.4/32.1 | 3.80 |
비교예 4 | 에그-쉘 | 1100 | 14.4 | 7.87 | 35.8/32.3 | 92.7/91.1 | 33.2/29.4 | 11.33 |
구분 | 담체 열처리온도 (℃) |
표면적 (m2/g) |
메조기공 부피 (cm3/g) |
기공 평균 크기 (Å) |
알루미나 담체 1 | 850 | 132 | 0.615 | 139 |
알루미나 담체 2 | 950 | 114 | 0.598 | 154 |
알루미나 담체 3 | 1050 | 91 | 0.524 | 170 |
알루미나 담체 4 | 1100 | 54 | 0.367 | 221 |
Claims (3)
- 경질탄화수소의 탈수소화 촉매반응에 사용되는 구형 탈수소화 촉매로서, 담체는 감마 알루미나 및 세타 알루미나의 혼합물로 구성되고, 백금 및 주석 합금 성분이 에그-쉘 형태로 존재하고, 칼륨은 균일하게 분포되는, 탈수소화 촉매.
- 제1항에 있어서, 상기 담체는 0.5~0.65cc/g의 기공부피를 가지는, 탈수소화 촉매.
- 제1항에 있어서, 상기 백금의 분산도는 30~50%이고, 백금-주석 합금의 평균 입자 크기는 3nm~5nm인, 탈수소화 촉매.
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KR20180124313A (ko) * | 2017-05-11 | 2018-11-21 | 희성촉매 주식회사 | 높은 재생 효율의 직쇄형 경질탄화수소류 탈수소화 촉매 제조방법 |
KR101981886B1 (ko) * | 2018-02-01 | 2019-05-23 | 효성화학 주식회사 | 탈수소화 촉매 |
KR20190123155A (ko) * | 2018-04-23 | 2019-10-31 | 효성화학 주식회사 | 알루미나 담체의 제조방법 |
KR20200044381A (ko) * | 2018-10-19 | 2020-04-29 | 희성촉매 주식회사 | 고효율의 분지형 경질탄화수소류 탈수소화 촉매 제조방법 |
KR20200091014A (ko) * | 2019-01-18 | 2020-07-30 | 효성화학 주식회사 | 촉매 담체의 제조방법 및 탈수소 촉매 |
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KR20180124313A (ko) * | 2017-05-11 | 2018-11-21 | 희성촉매 주식회사 | 높은 재생 효율의 직쇄형 경질탄화수소류 탈수소화 촉매 제조방법 |
KR101981886B1 (ko) * | 2018-02-01 | 2019-05-23 | 효성화학 주식회사 | 탈수소화 촉매 |
KR20190123155A (ko) * | 2018-04-23 | 2019-10-31 | 효성화학 주식회사 | 알루미나 담체의 제조방법 |
KR20200044381A (ko) * | 2018-10-19 | 2020-04-29 | 희성촉매 주식회사 | 고효율의 분지형 경질탄화수소류 탈수소화 촉매 제조방법 |
KR20200091014A (ko) * | 2019-01-18 | 2020-07-30 | 효성화학 주식회사 | 촉매 담체의 제조방법 및 탈수소 촉매 |
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