KR100365687B1 - Catalyst composition for dehydrogenating paraffin based hydrocarbon - Google Patents
Catalyst composition for dehydrogenating paraffin based hydrocarbon Download PDFInfo
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- KR100365687B1 KR100365687B1 KR1019950013118A KR19950013118A KR100365687B1 KR 100365687 B1 KR100365687 B1 KR 100365687B1 KR 1019950013118 A KR1019950013118 A KR 1019950013118A KR 19950013118 A KR19950013118 A KR 19950013118A KR 100365687 B1 KR100365687 B1 KR 100365687B1
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- platinum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 11
- 239000012188 paraffin wax Substances 0.000 title abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 abstract description 13
- 238000010517 secondary reaction Methods 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- INXLGDBFWGBBOC-UHFFFAOYSA-N platinum(2+);dicyanide Chemical compound [Pt+2].N#[C-].N#[C-] INXLGDBFWGBBOC-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/38—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
-
- B01J35/61—
-
- B01J35/63—
-
- B01J35/647—
Abstract
Description
본 발명은 불균일 촉매를 이용하여 파라핀계 탄화수소를 탈수소시켜 올레핀계 탄화수소로 전환하는 방법에 관한 것이다. 더 상세하게로는 높은 활성과 선택도 및 안정성을 갖는 탈수소용 촉매 조성물에 관한 것이다.The present invention relates to a process for dehydrogenating paraffinic hydrocarbons to olefinic hydrocarbons using heterogeneous catalysts. More particularly, the present invention relates to a catalyst composition for dehydrogenation having high activity, selectivity, and stability.
탈수소된 탄화수소는 정밀화학제품의 기초원료, 고분자 재료의 기초원료 및 고성능 휘발유의 제조를 위한 첨가제의 원료로 사용되는 경제성이 높은 화합물로서 이들에 대한 수요는 날로 높아지고 있다.Dehydrogenated hydrocarbons are highly economical compounds used as raw materials for fine chemicals, raw materials for polymer materials and additives for the production of high performance gasoline, and the demand for them is increasing day by day.
노말파라핀을 탈수소하여 노말올레핀으로 전환하는 방법은 이미 공지되어 있는 것으로서, 그 방법은 수소와 파라핀을 탈수소촉매와 접촉시키고 대기압 혹은 그 이상에서 고온으로 반응시키는 것이다. 이 반응에 사용되는 탈수소촉매로는 백금 또는 기타 Ⅷ B족 귀금속원소에 속하는 금속을 알루미나, 실리카, 실리카-알루미나 등에 담지시킨 것 등이 있다.The process of dehydrogenating normal paraffins to normal olefins is already known, which involves contacting hydrogen and paraffins with a dehydrogenation catalyst and reacting at high temperature at atmospheric pressure or above. Examples of the dehydrogenation catalyst used in this reaction include those in which a metal belonging to platinum or other Group B noble metal element is supported on alumina, silica, silica-alumina, or the like.
그러나 일반적으로 탈수소 공정에서는 열분해 반응, 이성질화 반응, 고리화반응 등의 2차적인 반응으로 인하여 목적생성물 이외의 것을 얻는 경우가 있으며, 탈수소 반응 자체가 더 진행되어 모노올레핀이 아닌 디올레핀이 생성되는 경우도있다.In general, however, dehydrogenation may yield other than the desired product due to secondary reactions such as pyrolysis, isomerization, and cyclization, and the dehydrogenation process may proceed further to produce diolefins other than monoolefins. There is also a case.
또한 조기에 촉매의 비활성화가 진행되어 촉매의 수명이 단축되고, 고온에서 반응을 시키면, 담체 표면에 분포된 백금 등의 금속입자들이 소결되어 활성 금속의 표면적이 감소되므로 이 역시 촉매 비활성화의 요인이 되기 때뮨에 탈수소 반응을 상업적 규모의 공정에 적용시에는 큰 부담이 되어 왔다.In addition, catalyst deactivation progresses prematurely, which shortens the life of the catalyst, and when the reaction is carried out at a high temperature, metal particles such as platinum distributed on the surface of the carrier are sintered to reduce the surface area of the active metal, which is also a factor of catalyst deactivation. At times, dehydrogenation has been a heavy burden when applied to commercial scale processes.
따라서 탈수소 공정용 촉매의 활성과 선택성을 향상시키기 위하여 백금 또는 기타 Ⅷ B족 귀금속 원소에 한가지 이상의 다른 금속 성분을 결합시킨 촉매 조성물이 종래부터 제안되어 왔다.Therefore, a catalyst composition in which at least one other metal component is combined with platinum or other Group VIII precious metal elements has been conventionally proposed to improve the activity and selectivity of the catalyst for dehydrogenation processes.
영국 특허 1,497,297호에는 갈륨, 인듐,탈륨 중에서 최소한 한가지 이상의 원소를 선택하여 백금 및 알칼리금속과 함께 알루미나에 담지시킨 촉매에 관해 기술하고 있으며, 영국 특허 1,499,297호에서는 백금 및 갈륨, 인듐 등과 알칼리 금속을 사용한 촉매계가 사용되고 있다. 또한 미국 특허 4,551,574호에는 백금, 주석, 인듐과 알칼리금속 또는 알칼리토금속을 다공성 지지체에 담지시킨 촉매 조성물에 대해 기술하고 있고 미국 특허 4,762,960호에는 백금, 주석,게르마늄,레늄 및 알칼리금속 또는 알칼리토금속을 옥사이드 지지체에 함침시킨 탈수소촉매에 관해 기술하고 있으며, 마지막으로 미국 특허 4,880,674호에는 백금, 팔라듐,이리듐, 오스뮴 및 ⅣA족 원소를 공침시킨 탈수소 촉매조성물에 관해 언급하고 있다.British Patent 1,497,297 describes a catalyst in which alumina is supported on alumina with at least one element selected from gallium, indium and thallium, and British Patent No. 1,499, 297 uses platinum, gallium, indium and alkali metals. A catalyst system is used. In addition, US Pat. No. 4,551,574 describes a catalyst composition in which platinum, tin, indium and alkali metals or alkaline earth metals are supported on a porous support, and US Pat. A dehydrogenation catalyst impregnated on a support is described, and finally US Pat. No. 4,880,674 refers to a dehydrogenation catalyst composition co-precipitated with platinum, palladium, iridium, osmium and Group IVA elements.
그러나 상기의 기술들에 의해 제조된 촉매들은 노말파라핀의 탈수소공정에서 나타나는 활성, 유용한 반응생성물의 선택성, 촉매의 안정성등의 측면에서 모두다 만족스럽지 못한 것이었다.However, the catalysts prepared by the above techniques were not all satisfactory in terms of activity in the dehydrogenation process of normal paraffin, selectivity of useful reaction products, and stability of the catalyst.
본 발명은 상기의 종래기술들의 문제점을 해결하기 위한 것으로서, 탈수소공정에서 2차적인 반응의 발생을 억제하고 목적 생성물의 선택성을 높이며 촉매의 안정성을 향상시키는 촉매 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the problems of the prior art, it is an object to provide a catalyst composition to suppress the occurrence of secondary reactions in the dehydrogenation process, to improve the selectivity of the desired product and to improve the stability of the catalyst.
본 발명자는 상기 목적을 달성하기 위하여 예의 연구한 결과, 백금(Pt), 주석(Sn), 티타늄(Ti)을 상호 임계적으로 결합하면 노말파라핀을 탈수소하여 노말올레핀으로 전환하는데 있어서, 높은 활성과 장시간의 활성 유지를 이룰수 있는 것을 알게되어 본발명을 완성하게 되었다.As a result of earnestly researching to achieve the above object, the present inventors found that when the platinum (Pt), tin (Sn), and titanium (Ti) are critically bound to each other, dehydrogenation of normal paraffins to convert to normal olefins, The present invention was found to be able to achieve long-term active maintenance.
즉 본 발명은 파라핀계 탄화수소 탈수소용 촉매 조성물을 제조함에 있어서, 구형의 알루미나를 주성분으로 하는 다공성 금속 산화물 담체에 함유 원소 기준으로 백금 0.2∼1.0 중량%, 주석 0.05∼0.5 중량%, 티타늄 0.05∼0.5 중량%, 그리고 알칼리금속 0.2∼2.0 중량%를 담지하되, 이 때 주석/티타늄의 중량비가 0.1∼10 이며, 백금/(주석+티타늄)의 중량비가 0.2∼10의 범위내에 있고, 또한 백금/알칼리금속의 중량비는 0.1∼5.0 임을 특징으로 한다.In the present invention, in preparing a catalyst composition for paraffinic hydrocarbon dehydrogenation, 0.2 to 1.0% by weight of platinum, 0.05 to 0.5% by weight of tin, and 0.05 to 0.5 of titanium based on the elements contained in a porous metal oxide carrier mainly composed of spherical alumina It is supported by weight percent and 0.2 to 2.0 weight percent alkali metal, wherein the weight ratio of tin / titanium is 0.1 to 10, the weight ratio of platinum / (tin + titanium) is in the range of 0.2 to 10, and also platinum / alkali The weight ratio of the metal is characterized in that 0.1 to 5.0.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 촉매에 적합한 지지체로는, 일반적으로 사용되는 200㎡/g 이상의 높은 비표면적을 가지면서 0.5cc/g ∼ 1.5cc/g의 층 다공용적을 갖는 알루미나와는 달리 촉매의 안정성 및 성능의 향상을 도모하기 위하여 85㎡/g이하의 표면적과 0.4cc/g -0.8cc/g의 층 다공용적을 갖는 알루미나를 사용한다. 한편 지지체로서 바람직한 형상은 직경 1.0 - 2.0mm의 구형 입자인 것이다.Suitable supports for the catalysts according to the present invention, unlike the alumina having a high specific surface area of at least 200 m 2 / g and having a pore volume of 0.5 cc / g to 1.5 cc / g, are generally used. Alumina having a surface area of 85 m 2 / g or less and a layer pore volume of 0.4 cc / g -0.8 cc / g is used for the purpose of improvement. On the other hand, the shape preferable as a support body is a spherical particle with a diameter of 1.0-2.0 mm.
알루미나를 구형으로 제조하기 위해서는 공지의 졸겔법이 적용 가능하다.In order to manufacture alumina into a spherical shape, a known sol-gel method can be applied.
즉, 알루미늄 출발물질을 적당한 해고제와 물과 함께 반응시켜 졸로 전환시키고, 이 졸 혼합물을 오일조중에 적하시켜 겔의 구형 입자를 형성한다. 또한 제조된 구형입자가 앞서 언급된 표면적, 다공 용적등의 물성을 갖도록 하기 위하여 1000℃이상의 고온에서 열처리를 하여준다.That is, the aluminum starting material is reacted with a suitable disinfectant and water to convert to a sol, and the sol mixture is dropped into an oil bath to form spherical particles of the gel. In addition, the prepared spherical particles are heat-treated at a high temperature of 1000 ° C. or more in order to have physical properties such as surface area and pore volume mentioned above.
본 발명의 촉매를 제조하기 위한 방법으로는 먼저 주석, 티타늄과 알루미나의 공겔화에 의해 주석, 티타늄 함유 알루미나를 제조하고 이것에 백금 그리고 알칼리금속을 공함침 또는 이단 함침등의 방법으로 제조한다.As a method for preparing the catalyst of the present invention, tin, titanium-containing alumina is first prepared by cogelation of tin, titanium and alumina, and platinum and alkali metal are co-impregnated or two-stage impregnation therein.
본 발명의 촉매 조성물의 주성분인 금속으로는 Ⅷ B족 귀금속원소. 즉 백금, 팔라듐, 이리듐, 로듐, 오스뮴,루테늄 등이 사용될 수 있는데 앞에서도 언급했듯이 가장 바람직한 원소로서 백금을 사용한다. 백금은 촉매 전체에 골고루 잘 분산되는 것이 바람직한데, 염화백금산, 시안화백금, 백금착염 등의 수용성 화합물을 백금분산에 영향을 미치는 극소량의 계면활성제와 함께 혼합하여 알루미나에 함침시킨다. 그렇게 하면 최종복합체 중에 균일하게 분산 또는 고착되게 된다.As a metal which is a main component of the catalyst composition of this invention, a Group B noble metal element. That is, platinum, palladium, iridium, rhodium, osmium, ruthenium, etc. may be used. As mentioned above, platinum is used as the most preferable element. Platinum is preferably dispersed evenly throughout the catalyst. Water-soluble compounds such as chloroplatinic acid, platinum cyanide, and platinum complex salts are mixed with a very small amount of surfactant affecting platinum dispersion and impregnated in alumina. Doing so causes uniform dispersion or fixation in the final composite.
본 발명의 촉매조성물을 구성하고 있는 다른 중요한 성분이 알칼리금속인데, 알칼리 금속에는 리튬, 나트륨, 칼륨, 세슘, 루비늄 등이 속한다. 이중 본 발명에서는 칼륨(K)과 마그네슘(Mg)를 칼륨/마그네슘=0.1 - 10의 중량비로 동시에 사용한다.Another important component constituting the catalyst composition of the present invention is an alkali metal, which belongs to lithium, sodium, potassium, cesium, rubinium and the like. In the present invention, potassium (K) and magnesium (Mg) are used simultaneously in the weight ratio of potassium / magnesium = 0.1-10.
본 발명에 의해 제조된 촉매를 이용한 탈수소 반응조건으로, 온도는 400℃ ~ 700℃이고, 반응 압력은 0.1 - 5기압의 범위를 들 수 있으며, 촉매와 탄화수소를 질소혹은 수소로 희석시킨 혼합기체와의 접촉시간을 액체 공간속도(LHSV : LiquidHourly Space Velocity)로 표시하면 0.1∼30hr-1이고, 코크 형성을 억제시키기 위해 탄화수소를 희석시키는데 사용된 질소, 수소 등의 분위기 기체의 혼합비 혹은 분압은, 혼합비로는 탄화수소 대비 몰비(수소 또는 질소/탄화수소)로 0.1∼5, 분압으로는 0∼0.16기압의 범위이다.Dehydrogenation reaction conditions using the catalyst prepared by the present invention, the temperature is 400 ℃ ~ 700 ℃, the reaction pressure may be in the range of 0.1 to 5 atm, and the mixed gas and dilution of the catalyst and hydrocarbon with nitrogen or hydrogen and When the contact time is expressed as LiquidHourly Space Velocity (LHSV), it is 0.1 to 30hr -1 . The furnace is in the range of 0.1 to 5 in molar ratio (hydrogen or nitrogen / hydrocarbon) relative to hydrocarbon, and 0 to 0.16 atm in partial pressure.
담체의 제조에 있어서 본 발명에서 강조되는 것은 알루미나 제조시 촉매 조성물의 일부 유효 금속을 공침시키는 것과 담체의 소성 조건이다.Emphasizing in the present invention in the preparation of the carrier is the coprecipitation of some effective metals of the catalyst composition in the preparation of alumina and the firing conditions of the carrier.
즉, 본 발명에서 강조되고 있는 담체의 특성은 촉매 전체의 특성에 중요한 영향을 미치므로 다음의 담체 제조 공정이 강조된다.That is, the characteristics of the carrier highlighted in the present invention have a significant influence on the properties of the entire catalyst, and the following carrier production process is emphasized.
본 발명에서 적용 우수한 효과를 나타내는 담체의 규격은 B.E.T법으로 측정된 표면적 85㎡/g이하, 총 기공 부피 0.4cc/g ∼0.8cc/g, 평균 기공반경 100∼150Å이며, 형태는 분말형, 구형, 판상형 등으로서, 바람직하게는 200메시 이하의 분말 또는 1∼2mm정도의 지름을 가진 구형 담체이며 반응기내의 충전밀도는 0.5∼1cc/g이다.The specification of the carrier which shows the excellent effect applied in the present invention is 85 m 2 / g or less, the total pore volume of 0.4cc / g ~ 0.8cc / g, the average pore radius of 100 ~ 150 측정 measured by BET method, the form is powder type, Spherical, plate-like, etc., preferably a powder of 200 mesh or less, or a spherical carrier having a diameter of about 1 to 2 mm, and a packing density in the reactor is 0.5 to 1 cc / g.
촉매의 코크 형성에 의한 비활성화를 억제하기 위해, 본 발명의 촉매는 반응물 기체 중에 유기황 내의 황 성분 기준으로 10 - 100 중량ppm 함유되도록 투입하여 반응을 시킨다.In order to suppress deactivation due to coke formation of the catalyst, the catalyst of the present invention is added to react with 10 to 100 ppm by weight of sulfur in organic sulfur based on the reactant gas.
이하 다음 실시예에서 본 반응 효과 및 그 구체적인 적용 방법에 대하여 설명하면 다음과 같으며, 실시예에서 본 발명에 의해 얻어질 수 있는 장점을 증명하기 위해 본 발명의 촉매 및 본 발명과 다른 촉매를 제조하였다.Hereinafter, the reaction effect and the specific application method of the present invention will be described as follows. In order to demonstrate the advantages that can be obtained by the present invention, the catalyst of the present invention and the catalyst different from the present invention are prepared. It was.
본 발명에 의해 제조된 촉매는 C3∼C20탄화수소의 탈수소 반응에서 높은 활성 및 선택성을 나타내었고, 장시간 사용에도 활성 및 선택도의 안정성을 나타내었다.The catalyst prepared by the present invention exhibited high activity and selectivity in the dehydrogenation of C 3 -C 20 hydrocarbons, and showed stability of activity and selectivity even with prolonged use.
[실시에 1,2,3][Examples 1,2,3]
먼저 금속성분을 담지하기 위한 담체를 제조하였다. 주석과 티타늄의 출발물질을 알루미나 졸과 함께 혼합하고 약염기인 헥사메틸렌 테트라아민(HMT)를 알루미나졸의 27 중량% 만큼 가하여 겔화시킨 다음 오일조 중에 적하시켜 일정한 모양을 갖는 담체를 얻었다. 이를 120℃에서 건조후 1000℃∼1200℃의 온도에서 소성시켜 주석, 티타늄 함유 알루미나를 제조하였다. 이렇게 제조된 알루미나에 백금 및 알칼리금속을 함침시켜 여러가지 촉매를 제조하였으며 이를 표 1에 나타내었다.First, a carrier for supporting a metal component was prepared. Starting materials of tin and titanium were mixed together with the alumina sol, gelled by adding 27% by weight of the weak base hexamethylene tetraamine (HMT), and then dropped in an oil bath to obtain a carrier having a uniform shape. It was dried at 120 ° C and calcined at a temperature of 1000 ° C to 1200 ° C to prepare tin and titanium-containing alumina. Thus prepared alumina was impregnated with platinum and alkali metal to prepare various catalysts, which are shown in Table 1.
각 촉매의 성능 비교를 위한 반응시험은 상압, 600℃에서 프로판(순도:99.9 중량%)을 탈수소 반응대상으로 하여 실험하였으며, LHSV는 3hr-1, 촉매량을 3g기준으로 하였다. 반응기는 촉매 작용이 거의 없는 석영으로 만든 고정층 반응기를 사용하였으며, 수소의 분압은 0.5 기압, 즉 수소 대 프로판의 몰비는 1로 고정하였다.Reaction test for comparing the performance of each catalyst was tested using a propane (purity: 99.9% by weight) dehydrogenation reaction at 600 ℃, atmospheric pressure, LHSV was 3hr -1 , the amount of the catalyst was based on 3g. The reactor used a fixed bed reactor made of quartz with almost no catalysis, and the partial pressure of hydrogen was fixed at 0.5 atm, ie the molar ratio of hydrogen to propane was 1.
[비교예 1,2][Comparative Examples 1,2]
기존의 기술에 의한 조성을 이용하여 측매를 제조하였고, 위와 동등한 조건 및 방법으로 시험하여 그 결과를 표 1에 같이 표시하였다.The side-solvent was prepared using the composition by the existing technique, and tested under the same conditions and methods as above, and the results are shown in Table 1.
[표1]Table 1
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| US4608360A (en) * | 1985-07-02 | 1986-08-26 | Uop Inc. | Dehydrogenation catalyst compositions and method of preparing same |
| KR890000516A (en) * | 1987-06-29 | 1989-03-15 | 게리 디. 스트리트 | Immunosuppressive peptide |
| US5143886A (en) * | 1990-02-07 | 1992-09-01 | Snamprogetti S.P.A. | Catalytic composition for the dehydrogenation of C2 -C5 paraffins |
| WO1994029021A1 (en) * | 1993-06-14 | 1994-12-22 | Den Norske Stats Oljeselskap A.S. | New catalyst, and processes for dehydrogenating dehydrogenatable hydrocarbons |
| KR100208560B1 (en) * | 1994-12-08 | 1999-07-15 | 전원중 | Catalyst composition for dehydrogenating paraffin hydrocarbon |
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| US4608360A (en) * | 1985-07-02 | 1986-08-26 | Uop Inc. | Dehydrogenation catalyst compositions and method of preparing same |
| KR890000516A (en) * | 1987-06-29 | 1989-03-15 | 게리 디. 스트리트 | Immunosuppressive peptide |
| US5143886A (en) * | 1990-02-07 | 1992-09-01 | Snamprogetti S.P.A. | Catalytic composition for the dehydrogenation of C2 -C5 paraffins |
| WO1994029021A1 (en) * | 1993-06-14 | 1994-12-22 | Den Norske Stats Oljeselskap A.S. | New catalyst, and processes for dehydrogenating dehydrogenatable hydrocarbons |
| KR100208560B1 (en) * | 1994-12-08 | 1999-07-15 | 전원중 | Catalyst composition for dehydrogenating paraffin hydrocarbon |
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| KR101456900B1 (en) * | 2013-12-04 | 2014-11-04 | 희성촉매 주식회사 | Preparation of dehydrogenation catalysts for hydrocarbons using surfatants |
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