KR20200048827A - High dispered noble metal alloy/carrier catalyst, and preparation method of catalyst - Google Patents
High dispered noble metal alloy/carrier catalyst, and preparation method of catalyst Download PDFInfo
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- KR20200048827A KR20200048827A KR1020180131357A KR20180131357A KR20200048827A KR 20200048827 A KR20200048827 A KR 20200048827A KR 1020180131357 A KR1020180131357 A KR 1020180131357A KR 20180131357 A KR20180131357 A KR 20180131357A KR 20200048827 A KR20200048827 A KR 20200048827A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 title claims description 11
- 239000000956 alloy Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 75
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229910000923 precious metal alloy Inorganic materials 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- FTIMWVSQXCWTAW-UHFFFAOYSA-N ruthenium Chemical compound [Ru].[Ru] FTIMWVSQXCWTAW-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 101150003085 Pdcl gene Proteins 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000010970 precious metal Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- -1 hydroxy ions Chemical class 0.000 description 4
- 239000012696 Pd precursors Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011240 wet gel Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012694 precious metal precursor Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021076 Pd—Pd Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/0066—
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
본 발명은 귀금속 합금/담체 촉매 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 귀금속 합금의 입도와 분산도를 개선하여 촉매활성이 향상된 귀금속 합금/담체 촉매 및 그 제조하는 방법에 관한 것이다.The present invention relates to a noble metal alloy / carrier catalyst and a method for manufacturing the same, and more particularly, to a noble metal alloy / carrier catalyst having improved catalytic activity by improving the particle size and dispersion degree of the noble metal alloy and a method for manufacturing the same.
귀금속 담지 촉매는 불포화된 유기 화합물의 선택적인 수소화에 널리 사용된다. 수소화 반응은 일반적으로 동일한 귀금속 부하 량을 갖는 촉매의 경우, 귀금속의 표면상에서 수행되므로, 촉매 중의 귀금속의 분산도가 클수록 및/또는 상기 촉매 중의 지지된 귀금속 결정자의 함량이 높을수록 및/또는 상기 촉매의 열 안정성이 양호할수록 상기 촉매의 활성이 높고 상기 촉매의 사용 수명이 길어진다.Precious metal supported catalysts are widely used for the selective hydrogenation of unsaturated organic compounds. Since the hydrogenation reaction is generally performed on the surface of the noble metal in the case of a catalyst having the same noble metal loading, the greater the degree of dispersion of the noble metal in the catalyst and / or the higher the content of the supported noble metal crystallites in the catalyst and / or the catalyst The better the thermal stability of, the higher the activity of the catalyst and the longer the service life of the catalyst.
그러나, 귀금속 화합물을 함유하는 용액을 활성탄 상에 직접 부하하는 경우, 귀금속의 매우 얇은 광택성 층이 상기 활성탄의 표면상에 급속히 나타날 것이다. 그 이유는 주로 상기 활성탄의 표면이 환원 그룹, 예를 들어 알데하이드 그룹 및 자유 전자를 가지며, 이들은 귀금속 이온을 귀금속으로 쉽게 환원시키기 때문이다. 그 결과, 상기와 같이 제조된 촉매는 매우 낮은 분산도의 귀금속을 갖는다. However, when a solution containing a noble metal compound is directly loaded onto activated carbon, a very thin glossy layer of the noble metal will rapidly appear on the surface of the activated carbon. This is mainly because the surface of the activated carbon has a reducing group, for example, an aldehyde group and free electrons, and these easily reduce precious metal ions to a precious metal. As a result, the catalyst prepared as described above has a very low dispersibility precious metal.
이에 따라, 대한민국 등록특허 '10-1117006'은 백금합금/담체 촉매의 제조방법을 기재하고 있으며, 이를 통해 제조된 촉매 및 연료전지 기술은 1단계로 금속의 수용성 및 유레아를 물에 용해, 담지체를 분산하고, 하이드록시 이온의 의해 분산용액 산도를 5-12 유지하고, 2단계로 60-120℃ 고온에서 침강시키고, 3단계로 액상환원 또는 분산용액에서 담지된 촉매를 수소분위기에서 기상환원시키는 단계를 포함하고 있다.Accordingly, Korean Patent Registration '10 -1117006 'describes a method of manufacturing a platinum alloy / carrier catalyst, and the catalyst and fuel cell technology produced through this is the first step in dissolving the water-soluble and urea of the metal in water and supporting it. Dispersing, maintaining the acidity of the dispersion solution 5-12 by hydroxy ions, sedimentation at a high temperature of 60-120 ° C in 2 steps, and in 3 steps, the catalyst supported in the liquid reduction or dispersion solution is subjected to gas phase reduction in a hydrogen atmosphere. It includes steps.
또한, 대한민국 등록특허 '10-1678225'는 백금계 촉매의 제조방법을 기재하고 있으며, 제조방법의 1단계로서 백금 금속염과 용매를 혼합하고, 무기 담지체를 첨가한 다음 2단계로서 백금 금속염 대비 10 내지 200 중량% 에폭사이드를 첨가한 다음 백금 금속입자를 형성하고 3단계로서 세척 및 건조하는 과정을 나타내고 있다.In addition, the Republic of Korea registered patent '10 -1678225 'describes a method of manufacturing a platinum-based catalyst, as a first step of the manufacturing method, mixing a platinum metal salt and a solvent, adding an inorganic carrier, and then adding the inorganic carrier 10 as a second step. After adding 200% by weight of epoxide, platinum metal particles are formed and washed and dried in three steps.
그러나 촉매 제조시 첨가제가 들어가며고 여전히 제조공정이 복잡하며, 백금의 분산도가 낮아 촉매 활성이 제대로 나타나지 않는 문제점이 있어, 제조공정이 간단하고 촉매 활성이 높은 귀금속 촉매 제조방법의 개발이 요구되고 있다.However, there is a problem that the catalyst activity is not properly exhibited due to the addition of additives in the preparation of the catalyst, the manufacturing process is still complicated, and the dispersion degree of platinum is low. Therefore, there is a need to develop a method for manufacturing a precious metal catalyst having a simple manufacturing process and high catalytic activity. .
상기 문제점을 해결하기 위하여, 본 발명은 귀금속 합금의 입도와 분산도를 개선하여 촉매활성이 향상된 귀금속 합금/담체 촉매의 제조방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a method of manufacturing a noble metal alloy / carrier catalyst with improved catalytic activity by improving the particle size and dispersion degree of a noble metal alloy.
또한, 본 발명은 상기 제조방법에 의해 제조된 고분산 귀금속 담지 촉매를 제공하는 것을 목적으로 한다. In addition, an object of the present invention is to provide a high-dispersion precious metal-carrying catalyst prepared by the above-described production method.
상기의 목적을 해결하기 위하여 본 발명은,The present invention to solve the above object,
(a) 귀금속 전구체 용액을 제조하는 단계;(a) preparing a noble metal precursor solution;
(b) 지지체를 첨가하는 단계;(b) adding a support;
(c) 침전제를 첨가하여 pH를 4.5 내지 11.5로 조절하는 단계;(c) adjusting the pH to 4.5 to 11.5 by adding a precipitant;
(d) 환원제를 첨가하는 단계; 및(d) adding a reducing agent; And
(e) 여과, 세척 및 건조하는 단계;를 포함하는 고분산 귀금속 합금/담체 촉매 제조방법을 제공한다.(e) filtration, washing and drying; provides a method for producing a highly dispersed precious metal alloy / carrier catalyst comprising a.
상기 귀금속은 플래티늄(Platinum), 팔라듐(Palladium), 루테늄(Ruthenium) 및 루비듐(Rubidium) 중에서 선택되는 하나 이상이다.The noble metal is one or more selected from platinum, palladium, ruthenium and rubidium.
상기 침전제를 첨가하는 단계에서 pH를 5.5 내지 9.5로 조절한다.In the step of adding the precipitant, the pH is adjusted to 5.5 to 9.5.
상기 침전제는 NaOH, Na2CO3 및 KOH 중에서 선택되는 하나 이상이며, 침전온도는 40℃ - 80℃이다.The precipitating agent is NaOH, Na 2 CO 3 and It is one or more selected from KOH, and the precipitation temperature is 40 ° C-80 ° C.
상기 환원제는 히드라진(N2H4), 소듐 보로히드라진(NaBH4), 소듐 포메이트(HCOONa) 및 포름알데히드(CH2O) 중에서 선택되는 어느 하나 이상이며, 환원온도는 40℃ - 80℃이다.The reducing agent is at least one selected from hydrazine (N 2 H 4 ), sodium borohydrazine (NaBH 4 ), sodium formate (HCOONa) and formaldehyde (CH 2 O), and the reduction temperature is 40 ° C-80 ° C. .
또한, 상기 지지체는 Al2O3이다.In addition, the support is Al 2 O 3 .
상기의 다른 목적을 해결하기 위하여 본 발명은,The present invention to solve the above other objects,
상기 제조방법에 의해 제조된 고분산 귀금속 합금/담체 촉매를 제공한다.Provided is a highly dispersed precious metal alloy / carrier catalyst prepared by the above manufacturing method.
상기 담체는 Gamma상, Gamma와 Eta의 혼합상, 및 Eta상을 가진 Al2O3 중에서 선택되는 어느 하나 이상을 소성하여 사용한다.The carrier is used by firing any one or more selected from Gamma phase, a mixed phase of Gamma and Eta, and Al 2 O 3 having an Eta phase.
상기 귀금속의 분산도는 20 내지 50 %이다.The degree of dispersion of the noble metal is 20 to 50%.
본 발명에 따른 귀금속 담지 촉매의 제조방법은 입자크기가 작으면서도 균일한 분포를 가지며 촉매 활성이 높은 촉매를 제조할 수 있고, 대량생산이 용이하므로, 종래의 귀금속 담지 촉매의 제조방법을 대신하여 유용하게 사용될 수 있다. The method for preparing a noble metal-supported catalyst according to the present invention is useful in place of the conventional method for preparing a noble metal-supported catalyst, because it can produce a catalyst having a small particle size, a uniform distribution and a high catalyst activity, and mass production is easy. Can be used.
또한, 본 발명에 따른 귀금속 담지 촉매의 제조방법에 의하면 간단한 공정으로 좁은 입자크기를 갖는 나노입자의 제조가 가능하며, 이러한 귀금속 담지 촉매는 정밀화학공정, 자동차 배기가스 촉매 및 연료전지의 전극물질 등에 유용하게 적용할 수 있다.In addition, according to the method for manufacturing a noble metal-carrying catalyst according to the present invention, it is possible to manufacture nanoparticles having a narrow particle size in a simple process. It can be usefully applied.
도 1a는 본 발명의 일 실시예에 따른 귀금속 담지 촉매의 제조 공정을 나타내는 모식도이다.
도 1b는 본 발명의 일 비교예에 따른 귀금속 담지 촉매의 제조 공정을 나타내는 모식도이다.
도 2는 본 발명의 일 실시예 및 비교예에 따라 제조된 플래티늄 담지 알루미나(Al2O3) 촉매의 침전제에 따른 반응을 도식화한 것이다.
도 3a은 본 발명의 일 실시예에 따라 제조된 플래티늄 담지 알루미나(Al2O3) 촉매(A)의 FE-TEM 이미지이다.
도 3b은 본 발명의 일 실시예에 따라 제조된 플래티늄 담지 알루미나(Al2O3) 촉매(B)의 FE-TEM 이미지이다.
도 3c은 본 발명의 일 실시예에 따라 제조된 팔라듐 담지 알루미나(Al2O3) 촉매(C)의 FE-TEM 이미지이다.
도 4a는 본 발명의 일 비교예에 따라 제조된 플래티늄 담지 알루미나(Al2O3) 촉매(D)의 FE-TEM 이미지 이다.
도 4b는 본 발명의 일 비교예에 따라 제조된 팔라듐 담지 알루미나(Al2O3) 촉매의(E)의 FE-TEM 이미지이다.1A is a schematic diagram showing a manufacturing process of a noble metal supported catalyst according to an embodiment of the present invention.
1B is a schematic view showing a process for producing a precious metal-supported catalyst according to a comparative example of the present invention.
Figure 2 is a diagram showing the reaction according to the precipitation agent of the platinum-supported alumina (Al 2 O 3 ) catalyst prepared according to an embodiment and a comparative example of the present invention.
3A is an FE-TEM image of a platinum-supported alumina (Al 2 O 3 ) catalyst (A) prepared according to an embodiment of the present invention.
3B is an FE-TEM image of a platinum-supported alumina (Al 2 O 3 ) catalyst (B) prepared according to an embodiment of the present invention.
3C is an FE-TEM image of a palladium-supported alumina (Al 2 O 3 ) catalyst (C) prepared according to an embodiment of the present invention.
4A is an FE-TEM image of a platinum-supported alumina (Al 2 O 3 ) catalyst (D) prepared according to a comparative example of the present invention.
4B is an FE-TEM image of (E) of a palladium-supported alumina (Al 2 O 3 ) catalyst prepared according to a comparative example of the present invention.
본 발명은 귀금속 합금/담체 촉매 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 귀금속 합금의 입도와 분산도를 개선하여 촉매활성이 향상된 귀금속 합금/담체 촉매 및 그 제조하는 방법에 관한 것이다. The present invention relates to a noble metal alloy / carrier catalyst and a method for manufacturing the same, and more particularly, to a noble metal alloy / carrier catalyst having improved catalytic activity by improving the particle size and dispersion degree of the noble metal alloy and a method for manufacturing the same.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 일측면에 따르면, (a) 귀금속 전구체 용액을 제조하는 단계; (b) 지지체를 첨가하는 단계; (c) 침전제를 첨가하여 pH를 4.5 내지 11.5로 조절하는 단계; (d) 환원제를 첨가하는 단계; 및 (e) 여과, 세척 및 건조하는 단계;를 포함하는 귀금속 담지 촉매의 고분산 제조방법을 제공한다.According to one aspect of the invention, (a) preparing a precious metal precursor solution; (b) adding a support; (c) adjusting the pH to 4.5 to 11.5 by adding a precipitant; (d) adding a reducing agent; And (e) filtration, washing and drying; provides a method for producing a highly dispersed precious metal-carrying catalyst comprising a.
먼저 귀금속 전구체 용액을 제조한다. 상기 귀금속 전구체 용액은 귀금속염 화합물을 무기산에 용해시킨 용액을 안정화제와 반응시킴으로써 제조할 수 있다.First, a precious metal precursor solution is prepared. The noble metal precursor solution can be prepared by reacting a solution in which a noble metal salt compound is dissolved in an inorganic acid with a stabilizer.
이때, 귀금속은 플래티늄(Platinum), 팔라듐(Palladium), 루테늄(Ruthenium) 및 루비듐(Rubidium)에서 하나 이상을 선택하는 것이 바람직하나, 이에 제한되는 것은 아니다. In this case, the precious metal is preferably selected from platinum, palladium, ruthenium and rubidium, but is not limited thereto.
또한, 귀금속 염은 상기 귀금속의 염기성 금속염으로서, 질산염, 아세트산염, 황산염, 염산염 등이 바람직하다. 또한 상기 무기산으로는 염산, 황산, 질산 및 인산으로 이루어지는 군으로부터 선택될 수 있으며, 바람직하게는 염산을 사용할 수 있다.Further, the noble metal salt is a basic metal salt of the noble metal, preferably nitrate, acetate, sulfate, hydrochloride, and the like. In addition, the inorganic acid may be selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and preferably hydrochloric acid.
전구체로 사용하는 H2PtCl6*6H2O 또는 H2PdCl4는 PtCl6 2- 또는 PdCl4 2- 의 음이온 상태의 착화합물 상태로 주로 존재한다. 촉매 제조시 금속과 지지체 사이의 상호인력은 촉매 특성에 많은 영향을 미친다. H 2 PtCl 6 * 6H 2 O or H 2 PdCl 4 used as a precursor mainly exists as an anionic complex of PtCl 6 2- or PdCl 4 2- . When preparing a catalyst, the mutual attraction between the metal and the support has a great influence on the catalyst properties.
지지체로는 Al2O3를 사용하는 것이 바람직하다. 일반적인 Al2O3는 다양한 전이상을 가진다. 이 중, 일반적으로 귀금속 또는 금속의 고분산 담지체로는 Gamma상을 가진 Al2O3를 주로 이용하며, 일부 Gamma와 Eta의 혼합상, 또는 Eta상을 가진 Al2O3를 소성하여 사용할 수 있다. It is preferable to use Al 2 O 3 as a support. Al 2 O 3 in general has various transition anomalies. Among these, Al 2 O 3 having a Gamma phase is mainly used as a high-dispersion carrier of a precious metal or a metal, and a mixed phase of some Gamma and Eta or Al 2 O 3 having an Eta phase can be calcined and used. .
알루미나(Al2O3)는 공침법(Co-precipitation Method), 주형법(Templating Method), 수열합성법(Hydrothermal Method) 및 에폭사이드 유도 졸-겔법(Epoxide-driven Sol-gel Method) 등에 의해 제조될 수 있으나, 에폭사이드 유도 졸-겔법이 알루미나 담체를 만드는데 있어 바람직하다. 예컨대 해당 방법을 통한 알루미나 담체의 제조는 ⅰ) 알코올 수용액에 알루미늄 전구체를 용해시켜 수화시키는 단계; ⅱ) 상기 용액에 에폭사이드계 화합물을 도입하여 수화된 알루미늄 이온에 수산화기(Hydroxyl Group)가 생기게 함과 동시에 축합반응을 진행하여 습윤 겔(Gel)을 얻는 단계; ⅲ) 상기 습윤 겔을 상온에서 숙성시키고 건조시키는 단계; ⅳ) 상기 건조된 습윤 겔을 열처리하는 단계를 포함할 수 있다. Alumina (Al 2 O 3 ) is prepared by a co-precipitation method, a templating method, a hydrothermal method, and an epoxide-driven sol-gel method. However, the epoxide-derived sol-gel method is preferred for making alumina carriers. For example, the preparation of the alumina carrier through the method includes: iii) hydrating by dissolving the aluminum precursor in an aqueous alcohol solution; Ii) introducing an epoxide-based compound into the solution to produce a hydroxyl group in a hydrated aluminum ion, and simultaneously performing a condensation reaction to obtain a wet gel; Iv) aging and drying the wet gel at room temperature; Iii) heat-treating the dried wet gel.
이때, 침전제 용액은 NaOH, KOH, NaHCO3 및 Na2CO3로 이루어지는 군으로부터 선택될 수 있으나, 이에 제한되는 것은 아니다.At this time, the precipitant solution may be selected from the group consisting of NaOH, KOH, NaHCO 3 and Na 2 CO 3 , but is not limited thereto.
본 발명의 제조방법을 적용하였을 때 H2PtCl6*6H2O 또는 H2PdCl4는 초기 pH값이 2-3을 나타내게 된다. 이 때, Al2O3 를 첨가할 때 pH 값은 2-3이 되기 때문에, Al2O3의 표면 전하 값은 양전하(+)가 된다. 따라서 H2PtCl6*6H2O 또는 H2PdCl4는 PtCl6 2- 또는 PdCl4 2-의 음의 전하(-)를 가진 착화합물 상태로 주로 존재하게 되고, Pt 또는 Pd 전구체와 Al2O3 사이의 상호인력 (+, -) 을 가진 상태에서 담지가 이루어지게 된다.When the manufacturing method of the present invention is applied, H 2 PtCl 6 * 6H 2 O or H 2 PdCl 4 has an initial pH value of 2-3. At this time, when Al 2 O 3 is added, the pH value becomes 2-3, so the surface charge value of Al 2 O 3 becomes positive charge (+). Therefore, H 2 PtCl 6 * 6H 2 O or H 2 PdCl 4 is mainly present as a complex compound having a negative charge (-) of PtCl 6 2- or PdCl 4 2- , Pt or Pd precursor and Al 2 O 3 Support is made in the state of having mutual manpower (+,-) between them.
침전제는 NaOH, Na2CO3 및 KOH 중에서 선택되는 하나 이상인 것이 바람직하며, pH 값은 5.5-9.5이며 침전온도는 40℃ - 80℃인 것이 바람직하다. 더 바람직하게는 pH 값은 7-8이며 침전온도는 60℃ - 70℃이다. pH와 온도는 Pt 또는 Pd의 입자성장 및 Pt-Al2O3 또는 Pd-Al2O3의 상호인력에 영향을 미치게 된다. pH 값이 5.5 미만 또는 침전온도가 40℃ 미만이면, 단일 Pt 또는 Pd의 입자크기는 작으나, Pt-Al2O3 또는 Pd-Al2O3 상호인력이 낮으므로 불균일한 분포 (입자간의 aggregation)를 나타낸다. 반면 pH 값이 9.5 초과 또는 침전온도 80℃가 초과되면, Pt-Al2O3 또는 Pd-Al2O3 상호인력이 강하므로, 불균일한 분포 (입자간의 aggregation)를 나타낸다. The precipitant is NaOH, Na 2 CO 3 and It is preferable that it is at least one selected from KOH, the pH value is 5.5-9.5, and the precipitation temperature is preferably 40 ° C-80 ° C. More preferably, the pH value is 7-8 and the precipitation temperature is 60 ° C-70 ° C. The pH and temperature affect the particle growth of Pt or Pd and the mutual attraction of Pt-Al 2 O 3 or Pd-Al 2 O 3 . If the pH value is less than 5.5 or the precipitation temperature is less than 40 ° C, the particle size of a single Pt or Pd is small, but the distribution of Pt-Al 2 O 3 or Pd-Al 2 O 3 is low, resulting in uneven distribution (aggregation between particles) Indicates. On the other hand, when the pH value exceeds 9.5 or the precipitation temperature exceeds 80 ° C, Pt-Al 2 O 3 or Pd-Al 2 O 3 has a strong mutual work force, and thus shows an uneven distribution (aggregation between particles).
환원제는 Hydrazine (N2H4), Sodium borohydride (NaBH4), Sodium formate (HCOONa) 및 Formaldehyde (CH2O) 중에서 선택되는 어느 하나 이상이며, 환원온도는 40℃ - 80℃이다. 또한, 환원제는 이들을 2종 이상 병용할 수도 있다.The reducing agent is at least one selected from Hydrazine (N 2 H 4 ), Sodium borohydride (NaBH 4 ), Sodium formate (HCOONa) and Formaldehyde (CH 2 O), and the reduction temperature is 40 ° C-80 ° C. Moreover, a reducing agent can also use these 2 or more types together.
구체적으로, 상기 단계는 반응기 내에서 교반 시키면서 귀금속 전구체 용액에 제조하고자 하는 촉매 내의 귀금속의 함량을 고려 후 계산하여 담지체를 투입한다. 그 후 침전제 용액을 이용하여 pH를 중성으로 조절하여 함침시키고 40 내지 80 ℃에서 0.5 내지 6시간 동안 교반시킴으로써 수행될 수 있다.Specifically, in the above step, the amount of the noble metal in the catalyst to be prepared in the noble metal precursor solution is taken into consideration while stirring in the reactor, and then the carrier is calculated and calculated. It can then be performed by impregnating by adjusting the pH to neutral using a precipitant solution and stirring at 40 to 80 ° C. for 0.5 to 6 hours.
본 발명의 다른 측면에 따르면, 상기 제조방법에 의해 제조된 귀금속 담지 촉매를 제공한다.According to another aspect of the present invention, there is provided a precious metal supported catalyst prepared by the above manufacturing method.
담체는 Gamma상, Gamma와 Eta의 혼합상, 및 Eta상을 가진 Al2O3 중에서 선택되는 어느 하나 이상을 소성하여 사용한다. 일반적인 Al2O3는 다양한 전이상을 가진다. 이 중, 일반적으로 귀금속 또는 금속의 고분산 담지체로는 Gamma상을 가진 Al2O3를 주로 이용하며, 일부 Gamma와 Eta의 혼합상, 또는 Eta상을 가진 Al2O3를 소성하여 사용할 수 있다. The carrier is used by firing any one or more selected from Gamma phase, a mixed phase of Gamma and Eta, and Al 2 O 3 having an Eta phase. Al 2 O 3 in general has various transition anomalies. Among these, Al 2 O 3 having a Gamma phase is mainly used as a high-dispersion carrier of a precious metal or a metal, and a mixed phase of some Gamma and Eta or Al 2 O 3 having an Eta phase can be calcined and used. .
본 발명의 고분산 귀금속 합금/담체 촉매에서 귀금속의 분산도는 20 내지 50 %이며, 바람직하게는 20 내지 40 %이다.The dispersion degree of the noble metal in the highly dispersed noble metal alloy / carrier catalyst of the present invention is 20 to 50%, preferably 20 to 40%.
이하, 바람직한 실시예를 들어 본 발명을 더욱 상세하게 설명한다. 그러나 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이에 의하여 제한되지 않는다는 것은 당업계의 통상의 지식을 가진 자에게 자명할 것이다. Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to illustrate the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereby.
<< 실시예>Example>
실시예 1. Pt/Example 1. Pt / AlAl 22 OO 33 촉매(A, B) 제조 : 전구체-지지체-침전제 Preparation of catalysts (A, B): precursor-support-precipitator
60 ℃의 온도에서 전구체 H2PtCl6*6H2O solution 13.5 mL가 포함된 용액에 지지체(담지체)인 Al2O3 0.95g을 첨가하고 3시간 동안 교반하여 혼합물을 제조하였다. 상기 단계에서 제조된 혼합물을 0.25 M의 수산화나트륨을 사용하여 pH 5.5 및 pH 7.5로 적정한 후, 400 rpm으로 3시간 교반하였다. 그리고 환원제인 0.3 M의 수소화 붕소나트륨 100 mL을 사용하여 액상환원을 수행하고 3시간 교반하였다. 그 후, 제조된 Pt/Al2O3 촉매를 여과하고, 105 ℃에서 2시간 동안 건조하여, 최종적으로 pH 5.5인 Pt/Al2O3 촉매(A)와 pH 7.5 Pt/Al2O3 촉매(B)를 제조하였다. 상기 과정을 도 1a에 도시하였다.To a solution containing 13.5 mL of the precursor H 2 PtCl 6 * 6H 2 O solution at a temperature of 60 ° C., 0.95 g of Al 2 O 3 as a support (carrier) was added and stirred for 3 hours to prepare a mixture. The mixture prepared in the above step was titrated to pH 5.5 and pH 7.5 using 0.25 M sodium hydroxide, and then stirred at 400 rpm for 3 hours. Then, liquid reduction was performed using 100 mL of 0.3 M sodium borohydride as a reducing agent and stirred for 3 hours. Thereafter, the prepared Pt / Al 2 O 3 catalyst was filtered, dried at 105 ° C. for 2 hours, and finally a Pt / Al 2 O 3 catalyst (A) having a pH of 5.5 and a pH 7.5 Pt / Al 2 O 3 catalyst (B) was prepared. The process is shown in Figure 1a.
실시예 2. Pd/AlExample 2. Pd / Al 22 OO 33 촉매(C) 제조 : 전구체-지지체-침전제 Preparation of catalyst (C): precursor-support-precipitator
60 ℃의 온도에서 전구체인 H2PdCl4 solution 13.5 mL가 포함된 용액에 지지체(담지체)인 Al2O3 0.95g을 첨가하고 3시간 동안 교반하여 혼합물을 제조하였다. 상기 단계에서 제조된 혼합물을 0.25 M의 수산화나트륨을 사용하여 pH 5.5로 적정한 후, 400 rpm으로 3시간 교반하였다. 이후 과정은 실시예 1과 동일하게 실시하였으며, 최종적으로 pH 5.5인 Pd/Al2O3 촉매(C)를 제조하였다. 상기 과정을 도 1a에 도시하였다.To a solution containing 13.5 mL of the precursor H 2 PdCl 4 solution at a temperature of 60 ° C., 0.95 g of Al 2 O 3 as a support (carrier) was added and stirred for 3 hours to prepare a mixture. The mixture prepared in the above step was titrated to pH 5.5 using 0.25 M sodium hydroxide, and then stirred at 400 rpm for 3 hours. Subsequently, the procedure was performed in the same manner as in Example 1, and finally, a Pd / Al 2 O 3 catalyst (C) having a pH of 5.5 was prepared. The process is shown in Figure 1a.
실시예 3. Pt/AlExample 3. Pt / Al 22 OO 33 및 Pd/Al And Pd / Al 22 OO 3 3 촉매(A, B, C)의 활성측정Measurement of catalyst (A, B, C) activity
상기 실시예에 따라 제조된 촉매의 활성을 측정하기 위하여 CO-chemisorption를 이용하여 제조된 촉매의 분산도를 측정하였다.To measure the activity of the catalyst prepared according to the above example, the dispersion degree of the prepared catalyst was measured using CO-chemisorption.
실시예 4. Pt/AlExample 4. Pt / Al 22 OO 33 및 Pd/Al And Pd / Al 22 OO 33 촉매(A, B, C)의 FE-TEM 분석 FE-TEM analysis of catalysts (A, B, C)
FE-TEM을 이용하여 상기 실시예에 따라 제조된 촉매의 크기를 확인하였다.The size of the catalyst prepared according to the above example was confirmed using FE-TEM.
비교예 1. Pt/AlComparative Example 1. Pt / Al 22 OO 33 촉매(D) 제조 : 전구체-침전제-지지체 Preparation of catalyst (D): precursor-precipitator-support
60 ℃의 온도에서 전구체인 H2PtCl6*6H2O solution 13.5 mL가 포함된 용액에 0.25 M의 수산화나트륨을 사용하여 pH 7.5로 적정하였다. 그 후 지지체(담지체)인 Al2O3 0.95g을 첨가하고 3시간 동안 교반하여 혼합물을 제조하였다. 이후 과정은 실시예 1과 동일하게 실시하였으며, 최종적으로 pH 7.5인 Pt/Al2O3 촉매(D)를 제조하였다. 상기 과정을 도 1b에 도시하였다.A solution containing 13.5 mL of the precursor H 2 PtCl 6 * 6H 2 O solution at a temperature of 60 ° C. was titrated to pH 7.5 using 0.25 M sodium hydroxide. Thereafter, 0.95 g of Al 2 O 3 as a support (carrier) was added and stirred for 3 hours to prepare a mixture. Subsequently, the procedure was performed in the same manner as in Example 1, and finally, a Pt / Al 2 O 3 catalyst (D) having a pH of 7.5 was prepared. The process is shown in Figure 1B.
비교예 2. Pd/AlComparative Example 2. Pd / Al 22 OO 33 촉매(E) 제조 : 전구체-침전제-지지체 Preparation of catalyst (E): precursor-precipitator-support
60 ℃의 온도에서 전구체인 H2PdCl4 solution 13.5 mL가 포함된 용액에 0.25 M의 수산화나트륨을 사용하여 pH 5.5으로 적정하였다. 그 후 지지체(담지체)인 Al2O3 0.95g을 첨가하고 3시간 동안 교반하여 혼합물을 제조하였다. 이후 과정은 실시예 1과 동일하게 실시하였으며, 최종적으로 pH 5.5인 Pd/Al2O3 촉매(E)를 제조하였다. 상기 과정을 도 1b에 도시하였다.The solution containing 13.5 mL of the precursor H 2 PdCl 4 solution at a temperature of 60 ° C. was titrated to pH 5.5 using 0.25 M sodium hydroxide. Thereafter, 0.95 g of Al 2 O 3 as a support (carrier) was added and stirred for 3 hours to prepare a mixture. Subsequently, the procedure was performed in the same manner as in Example 1, and finally, a Pd / Al 2 O 3 catalyst (E) having a pH of 5.5 was prepared. The process is shown in Figure 1B.
비교예 3. Pt/AlComparative Example 3. Pt / Al 22 OO 33 및 Pd/Al And Pd / Al 22 OO 33 촉매(D, E)의 활성 측정 Measurement of catalyst (D, E) activity
상기 비교예에 따라 제조된 촉매의 활성을 측정하기 위하여 CO-chemisorption를 이용하여 제조된 촉매의 분산도를 측정하였다.In order to measure the activity of the catalyst prepared according to the comparative example, the dispersion degree of the catalyst prepared using CO-chemisorption was measured.
비교예 4. Pt/AlComparative Example 4. Pt / Al 22 OO 33 및 Pd/Al And Pd / Al 22 OO 33 촉매(D, E)의 FE-TEM 분석 FE-TEM analysis of catalysts (D, E)
FE-TEM을 이용하여 상기 비교예에 따라 제조된 촉매의 크기를 확인하였다.The size of the catalyst prepared according to the comparative example was confirmed using FE-TEM.
<평가 및 결과><Evaluation and Results>
결과 1. Pt/AlResult 1. Pt / Al 22 OO 33 및 Pd/Al And Pd / Al 22 OO 33 촉매(A, B, C, D, E)의 활성 측정 Measurement of catalyst (A, B, C, D, E) activity
실시예 및 비교예 에 따라 제조된 Pt/Al2O3 및 Pd/Al2O3 촉매(A, B, C, D, E)의 활성을 측정하기 위하여 각각 CO-chemisorption 분석을 이용하여 CO 가스 흡착량, 금속 표면적, 금속 분산도 및 입자크기를 확인하였으며, 그 결과를 하기 표 1로 나타내었다.CO gas using CO-chemisorption analysis, respectively, to measure the activity of Pt / Al 2 O 3 and Pd / Al 2 O 3 catalysts (A, B, C, D, E) prepared according to Examples and Comparative Examples Adsorption amount, metal surface area, metal dispersion degree and particle size were confirmed, and the results are shown in Table 1 below.
그 결과, Pt/Al2O3 촉매(A, B, D)는 B, A, D 순서로 촉매 활성이 높은 것으로 나타났다. 즉, pH 7.5에서 제조된 Pt/Al2O3 촉매(B)가 가장 높은 분산도와 표면적, CO 가스 흡착량을 나타내고 입자크기 또한 가장 작은 것을 확인하였으며, pH 5.5에서 제조된 Pt/Al2O3 촉매(A)가 그 다음으로 활성이 높은 것으로 확인되었다. 또한, Pt/Al2O3 촉매(B, D)는 pH 7.5에서 제조된 점에서 동일하나 B가 D보다 촉매 활성이 우수한 것으로 나타났다.As a result, Pt / Al 2 O 3 catalysts (A, B, D) were found to have high catalytic activity in the order of B, A, D. That is, it was confirmed that the Pt / Al 2 O 3 catalyst (B) prepared at pH 7.5 showed the highest dispersion, surface area, and CO gas adsorption, and the smallest particle size, and the Pt / Al 2 O 3 prepared at pH 5.5. It was confirmed that the catalyst (A) was the next highest in activity. In addition, Pt / Al 2 O 3 catalysts (B, D) were the same in that they were prepared at pH 7.5, but B was found to have better catalytic activity than D.
또한, Pd/Al2O3 촉매(C, E)는 C가 E보다 촉매활성이 월등히 높은 것으로 나타났다. C와 E는 pH 5.5에서 제조된 점은 동일하나 제조 시 침전제와 지지체의 첨가 순서가 다르다.In addition, Pd / Al 2 O 3 catalysts (C, E) showed that C had significantly higher catalytic activity than E. C and E are the same in that they were prepared at pH 5.5, but the order of addition of the precipitant and the support during production is different.
이러한 결과는 촉매의 제조 환경의 차이에 한 것으로, 촉매 제조 시 pH가 중성에 가까우며, 촉매가 전구체-지지체-침전제 순서로 제조될 경우 활성이 높아진다는 것을 나타낸다.These results are due to differences in the production environment of the catalyst, and indicate that the pH is close to neutral when the catalyst is prepared, and the activity is increased when the catalyst is prepared in the order of precursor-support-precipitator.
Size (nm)Size (nm)
결과 2. Pt/Al
실시예 및 비교예에 따라 제조된 Pt/Al2O3 및 Pd/Al2O3 촉매(A, B, C, D, E) 의 FE-TEM 분석 결과를 도 3a 내지 도 4b에 도시하였다.The results of FE-TEM analysis of Pt / Al 2 O 3 and Pd / Al 2 O 3 catalysts (A, B, C, D, E) prepared according to Examples and Comparative Examples are shown in FIGS. 3A to 4B.
도 3a는 실시예 1에 따라 제조된 Pt/Al2O3 촉매(A)의 사진이며, 도 3b는 실시예 1에 따라 제조된 Pt/Al2O3 촉매(B)의 사진이고, 도 4a는 비교예 1에 따라 제조된 Pt/Al2O3 촉매(D)의 FE-TEM 사진이다. Figure 3a is a picture of the Pt / Al 2 O 3 catalyst (A) prepared according to Example 1, Figure 3b is a picture of the Pt / Al 2 O 3 catalyst (B) prepared according to Example 1, Figure 4a Is a FE-TEM photo of the Pt / Al 2 O 3 catalyst (D) prepared according to Comparative Example 1.
도 3c는 실시예 2에 따라 제조된 Pd/Al2O3 촉매(C)의 사진이며, 도 4b는 비교예 2에 따라 제조된 Pd/Al2O3 촉매(E)의 FE-TEM 사진이다. Figure 3c is a picture of a Pd / Al 2 O 3 catalyst (C) prepared according to Example 2, Figure 4b is a FE-TEM picture of a Pd / Al 2 O 3 catalyst (E) prepared according to Comparative Example 2 .
도 3a 내지 도 4b에 나타낸 바와 같이, 본 발명의 실시예에 따라 제조된 촉매의 경우, 약 2 내지 5 nm의 균일한 입자크기 분포를 가진다. 그러나 FE-TEM 이미지를 분석한 결과, pH 7.5 촉매(B)에서 pH 5.5 촉매(A)보다 높은 분산도를 나타내는 것을 확인할 수 있었으며, 같은 pH 조건에서 촉매 C의 분산도가 촉매매 B의 분산도 보다 높은 것을 확인할 수 있었다.3A to 4B, in the case of a catalyst prepared according to an embodiment of the present invention, it has a uniform particle size distribution of about 2 to 5 nm. However, as a result of analyzing the FE-TEM image, it was confirmed that the pH 7.5 catalyst (B) showed a higher dispersion than the pH 5.5 catalyst (A), and the dispersion degree of the catalyst C under the same pH condition was that of the catalyst medium B. It was confirmed that it was higher.
또한, 본 발명의 비교예에 따라 제조된 촉매(D, E)의 경우, 약 10 - 20 nm의 입자크기를 나타내며, FE-TEM 이미지에서 금속이 거의 분산되지 못하고 응집되어 있는 것을 확인할 수 있었다.In addition, in the case of the catalysts (D, E) prepared according to the comparative example of the present invention, it exhibited a particle size of about 10-20 nm, and it was confirmed that metal was hardly dispersed and aggregated in the FE-TEM image.
실시예에 따른 제조방법을 적용하였을 때 H2PtCl6*6H2O 또는 H2PdCl4는 초기 pH값이 2-3을 나타낸다. 이 때 Al2O3 를 첨가할 때 pH 값은 2-3이 되기 때문에, Al2O3의 표면 전하값은 양전하(+)이다. 따라서 H2PtCl6*6H2O 또는 H2PdCl4는 PtCl6 2- 또는 PdCl4 2- 의 음의 전하(-)를 가진 착화합물 상태로 우세하게 존재하기 때문에 Pt 또는 Pd 전구체와 Al2O3 사이의 상호인력 (+, -) 을 가진 상태에서 담지가 이루어진다.When applying the manufacturing method according to the embodiment H 2 PtCl 6 * 6H 2 O or H 2 PdCl 4 has an initial pH value of 2-3. At this time, since the pH value becomes 2-3 when Al 2 O 3 is added, the surface charge value of Al 2 O 3 is positive charge (+). Therefore, H 2 PtCl 6 * 6H 2 O or H 2 PdCl 4 is predominantly present as a complex with a negative charge (-) of PtCl 6 2- or PdCl 4 2- , so Pt or Pd precursor and Al 2 O 3 Support is made in the state of having mutual interactions (+,-) between them.
반면 비교예에 따른 제조방법의 경우, H2PtCl6*6H2O 또는 H2PdCl4의 전구체를 NaOH 용액을 이용하여, Pt(OH)2 또는 Pd(OH)2 등의 hydroxide 형태를 만든 후 Al2O3를 첨가한다. 이때 Al2O3 를 첨가할 때 pH 값은 Isoelectric point (표면의 전하가 0인 지점)에 근접하게 된다. 따라서, 1) Al2O3 표면전하 값이 0에 다가감에 따라 Pd 또는 Pt와의 상호인력이 작용이 어렵다. 2) Pt 또는 Pd 전구체와 Al2O3 사이의 상호인력보다 Pt-Pt 또는 Pd-Pd 사이의 상호인력이 더 크다. 따라서, Pd 또는 Pt의 분산도는 낮으며, 입자크기는 크게 된다.On the other hand, in the case of the preparation method according to the comparative example, after the precursor of H 2 PtCl 6 * 6H 2 O or H 2 PdCl 4 is formed using NaOH solution, hydroxide forms such as Pt (OH) 2 or Pd (OH) 2 are formed. Al 2 O 3 is added. At this time, when Al 2 O 3 is added, the pH value approaches the isoelectric point (the point where the charge on the surface is 0). Therefore, 1) Al 2 O 3 As the surface charge value approaches 0, it is difficult to interact with Pd or Pt. 2) The mutual attraction between Pt-Pt or Pd-Pd is greater than the mutual attraction between Pt or Pd precursor and Al 2 O 3 . Therefore, the dispersion degree of Pd or Pt is low, and the particle size becomes large.
상술한 바와 같이 본 발명에 따른 귀금속 촉매의 제조방법은 작고 균일한 입자크기 분포를 가지며 백금의 분산도가 높아 촉매 활성이 높은 촉매를 제조할 수 있다. 또한, 액체상태의 환원제를 이용하므로 종래의 지지체를 준비하는 단계에서, 분산제, 접착제 또는 이들의 혼합물을 혼합하는 과정인 담지체의 분산공정이 제거되어 공정이 단순해져 대량생산이 용이하므로, 종래의 귀금속 담지 촉매의 제조방법을 대신하여 유용하게 사용될 수 있다. 이와 같이 본 발명에 따른 귀금속 담지 촉매의 고분산 제조방법은 귀금속 담지촉매 제조 시 촉매 분산단계 없이도 높은 분산도를 기대할 수 있다.As described above, the method for producing a noble metal catalyst according to the present invention can produce a catalyst having a small and uniform particle size distribution and a high degree of catalytic dispersion of platinum. In addition, since a reducing agent in a liquid state is used, in the step of preparing the conventional support, the dispersion process of the carrier, which is the process of mixing the dispersing agent, the adhesive, or a mixture thereof, is eliminated, and the process is simplified to facilitate mass production. It can be usefully used in place of a method for producing a precious metal-supported catalyst. As described above, in the method for preparing a highly dispersed precious metal-supported catalyst according to the present invention, it is possible to expect a high degree of dispersion without a catalyst dispersion step in preparing a precious metal-supported catalyst.
이제까지 본 발명에 대하여 그 바람직한 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.So far, the present invention has been focused on the preferred embodiments. Those skilled in the art to which the present invention pertains will appreciate that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered in terms of explanation, not limitation. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent range should be construed as being included in the present invention.
Claims (9)
(b) 지지체를 첨가하는 단계;
(c) 침전제를 첨가하여 pH를 4.5 내지 11.5로 조절하는 단계;
(d) 환원제를 첨가하는 단계; 및
(e) 여과, 세척 및 건조하는 단계;를 포함하는 고분산 귀금속 합금/담체 촉매 제조방법.(a) preparing a noble metal precursor solution;
(b) adding a support;
(c) adjusting the pH to 4.5 to 11.5 by adding a precipitant;
(d) adding a reducing agent; And
(e) filtration, washing and drying; high dispersion precious metal alloy / carrier catalyst production method comprising a.
상기 귀금속은 플래티늄(Platinum), 팔라듐(Palladium), 루테늄(Ruthenium) 및 루비듐(Rubidium) 중에서 선택되는 하나 이상인 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매 제조방법.According to claim 1,
The noble metal is a platinum (Platinum), palladium (Palladium), characterized in that at least one selected from ruthenium (Ruthenium) and rubidium (Rubidium), high dispersion precious metal alloy / carrier catalyst manufacturing method.
상기 침전제를 첨가하는 단계에서 pH를 5.5 내지 9.5로 조절하는 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매 제조방법.According to claim 1,
In the step of adding the precipitating agent, characterized in that the pH is adjusted to 5.5 to 9.5, high dispersion precious metal alloy / carrier catalyst production method.
상기 침전제는 NaOH, Na2CO3 및 KOH 중에서 선택되는 하나 이상이며, 침전온도는 40℃ - 80℃인 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매 제조방법.According to claim 1,
The precipitating agent is NaOH, Na 2 CO 3 and One or more selected from KOH, characterized in that the precipitation temperature is 40 ℃-80 ℃, high dispersion precious metal alloy / carrier catalyst manufacturing method.
상기 환원제는 히드라진(N2H4), 소듐 보로히드라진(NaBH4), 소듐 포메이트(HCOONa) 및 포름알데히드(CH2O) 중에서 선택되는 어느 하나 이상이며, 환원온도는 40℃ - 80℃인 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매 제조방법.According to claim 1,
The reducing agent is any one or more selected from hydrazine (N 2 H 4 ), sodium borohydrazine (NaBH 4 ), sodium formate (HCOONa) and formaldehyde (CH 2 O), the reduction temperature is 40 ℃-80 ℃ Characterized in that, high dispersion precious metal alloy / carrier catalyst manufacturing method.
상기 지지체는 Al2O3인 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매 제조방법.According to claim 1,
The support is characterized in that the Al 2 O 3 , high dispersion precious metal alloy / carrier catalyst production method.
상기 담체는 Gamma상, Gamma와 Eta의 혼합상, 및 Eta상을 가진 Al2O3 중에서 선택되는 어느 하나 이상을 소성하여 사용하는 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매.The method of claim 7,
The carrier is characterized by using at least one selected from Al 2 O 3 having a Gamma phase, a mixed phase of Gamma and Eta, and an Eta phase, a highly dispersed precious metal alloy / carrier catalyst.
상기 귀금속의 분산도가 20 내지 50 %인 것을 특징으로 하는, 고분산 귀금속 합금/담체 촉매.The method of claim 7,
Characterized in that the dispersion degree of the noble metal is 20 to 50%, high dispersion noble metal alloy / carrier catalyst.
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