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WO2010076928A1 - 탈수소화 촉매 - Google Patents

탈수소화 촉매 Download PDF

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Publication number
WO2010076928A1
WO2010076928A1 PCT/KR2009/002739 KR2009002739W WO2010076928A1 WO 2010076928 A1 WO2010076928 A1 WO 2010076928A1 KR 2009002739 W KR2009002739 W KR 2009002739W WO 2010076928 A1 WO2010076928 A1 WO 2010076928A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
dehydrogenation
dehydrogenation catalyst
platinum
carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2009/002739
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English (en)
French (fr)
Inventor
최진순
김원일
고형림
최영교
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hyosung Corp
Original Assignee
Hyosung Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hyosung Corp filed Critical Hyosung Corp
Priority to ES201190044A priority Critical patent/ES2388863B2/es
Priority to CN2009801534272A priority patent/CN102271806A/zh
Priority to US13/142,506 priority patent/US8993474B2/en
Priority to RU2011127547/04A priority patent/RU2470704C1/ru
Publication of WO2010076928A1 publication Critical patent/WO2010076928A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • the present invention relates to a dehydrogenation catalyst having a macropore size and a high active density of platinum, which is used for the dehydrogenation of hydrocarbon gas.
  • the dehydrogenation reaction of the hydrocarbon gas proceeds at a high temperature of 550 ° C. or higher.
  • side reactions to it entail pyrolysis and coke formation reactions, and the extent of these side reactions is a key factor in determining the selectivity and activity of the catalyst.
  • the coke formation reaction one of the side reactions, lowers the overall reaction conversion rate by blocking the contact with the reactants by covering the active material on the catalyst with coke.
  • the inlet of the pores present in the catalyst is blocked, so that the active material present in the pores is rendered ineffective, thereby rapidly promoting inactivation.
  • hydrocarbon dehydrogenation catalysts Another requirement for hydrocarbon dehydrogenation catalysts is thermal stability.
  • the high temperature reaction temperature and the heat generated during the coke regeneration of the catalyst lead to thermal deformation and structural sintering of the catalyst itself, resulting in a change in catalyst reactivity.
  • the structural suitability of the catalyst, the thermal stability of the catalyst structure, the thermal stability of the active ingredient, and the coke regeneration of the catalyst are the key factors in determining a good catalyst.
  • dehydrogenation catalysts fall into two classes: chromium oxide catalysts and platinum catalysts.
  • Chromium-based catalysts (US Pat. No. 6,797,850) have a faster catalyst deactivation rate due to coke formation and a faster regeneration rate, resulting in shorter catalyst life compared to platinum-based catalysts and inherent problems due to the toxicity of chromium itself. Doing.
  • the platinum-based catalysts there is a catalyst having an outer layer containing an active ingredient of 40 ⁇ 160 ⁇ m, the inside is based on gamma-alumina (US Pat. No. 6,756,515) or alpha-alumina (US Pat. No. 6,486,370), respectively.
  • gamma-alumina US Pat. No. 6,756,515
  • alpha-alumina US Pat. No. 6,486,370
  • the metal active ingredient does not exist in the inner layer that determines the specific surface area of the catalyst by the pores, so that it may have characteristics having low dispersion and low active area.
  • alpha-alumina is a precious metal due to the low specific surface area. It shows a low catalytic activity by lowering the dispersibility of and reducing the overall active area of the precious metal.
  • platinum-based catalysts may be prepared using silica (US Pat. No. 7,432,406), zeolites or boron silicates (US Pat. No. 6,555,724), but these catalysts basically have pores having an average pore diameter of 10 nm or less. This makes it very sensitive to structural closure due to coke formation, which can lead to rapid deactivation of the catalyst.
  • the content of the active ingredient and the type of the carrier of the catalyst is the mainstream, the content of the pore distribution, which is one of the physical characteristics of the catalyst has not yet existed.
  • the pore volume and pore size are the major factors that determine the mass transfer coefficients of the reactants and products.In a fast chemical reaction rate, the diffusion resistance of the material determines the overall reaction rate. It may be advantageous to maintain high activity, and the use of a carrier having a large pore size may act insensitive to accumulation of coke and may be advantageous for maintaining catalytic activity.
  • the inventors of the present invention are studying a dehydrogenation catalyst having a macropore size and excellent catalyst activity, selectivity, and coke stability, while thermally deforming a dehydrogenation catalyst having a macropore size and a high active density of platinum. It was prepared by an adsorption method of room temperature / elevated temperature using an alumina carrier, and as a result of performing dehydrogenation of propane using the catalyst prepared above, it was confirmed that the conversion, selectivity, and yield were high, and the present invention was completed.
  • the present invention seeks to provide a dehydrogenation catalyst having a macropore size and a high active density of platinum, which is used for the dehydrogenation of hydrocarbon gases.
  • 1 is a view showing the results of measuring the crystallinity of the alumina of the catalysts B and D according to the present invention using X-ray analysis.
  • FIG. 2 is a view of the cross-sectional view of the catalysts B and D according to the present invention with a scanning electron microscope.
  • FIG. 3 is a diagram showing propane conversion and propylene selectivity in the product after the reaction by dehydrogenation of propane using the catalysts B and D according to the present invention and analyzed by gas chromatography.
  • the present invention is a catalyst used in the dehydrogenation reaction of hydrocarbon gas, platinum, auxiliary metal, alkali metal or alkaline earth metal, and a halogen component is supported on the carrier, the carrier is meso pore of 5 ⁇ 100nm and It has a macropore of 0.1-20 micrometers, and provides the dehydrogenation catalyst characterized by the active density of platinum being 0.001-0.009 weight% / m ⁇ 2>.
  • the hydrocarbon is a C 2 -C 5 linear hydrocarbon or ethylbenzene.
  • 0.05 to 1.5% by weight of platinum, 0.05 to 2.0% by weight of auxiliary metal, 0.05 to 3.0% by weight of alkali metal or alkaline earth metal, and 0.1 to 3.0% by weight of halogen component are added to the carrier. It is prepared by supporting the room temperature / elevated temperature adsorption.
  • the platinum is used as the main metal, and the auxiliary metal is selected from the group consisting of tin, germanium, gallium, indium, zinc and manganese, and tin is particularly preferable.
  • Alkali or alkaline earth metals are used selected from the group consisting of calcium, potassium, sodium, magnesium, lithium, strontium, barium, radium and beryllium.
  • As the halogen component one selected from the group consisting of chlorine, phosphorus and fluorine is used, and chlorine is particularly preferable.
  • the carrier may be alumina, silica and mixed components thereof, preferably alumina.
  • Theta crystallinity of alumina is a factor that determines the degree of coke formation, and preferably 90% or more.
  • the carrier has a specific surface area of 50 to 170 m 2 / g, and has meso pores of 5 to 100 nm and macro pores of 0.1 to 20 ⁇ m. If the specific surface area of the carrier is less than 50 m 2 / g, the dispersibility of the metal active component is lowered. If the specific surface area is more than 170 m 2 / g, the gamma crystallinity of the alumina is kept high, thereby increasing the side reactivity.
  • the volume of the pores of the carrier and the size of the pores are the major factors that determine the mass transfer coefficients of the reactants and products.
  • the diffusion resistance of the material determines the overall reaction rate, so that the structure of the large pores Is advantageous for keeping the activity of the catalyst high. Therefore, the use of a carrier having a large pore size is insensitive to the accumulation of coke, and the high mass transfer rate results in high reaction activity even with an increase in the liquid hourly space velocity (LHSV).
  • LHSV liquid hourly space velocity
  • a macropore of 10 nm or more has a pore of 10 nm or more.
  • the dehydrogenation catalyst according to the present invention is a catalyst having a high dispersion degree of platinum, and the active density of platinum acting as an active point is preferably 0.001 to 0.009 wt% / m 2. If the active density of platinum is less than 0.001% by weight / m2, the active point is not enough, the reaction conversion rate is lowered, and if it exceeds 0.009% by weight / platinum, the dispersion of platinum is lowered, the amount of coke is increased and the side reactivity is increased. The selectivity is lowered. Platinum's active density is a key factor in determining particle size. The distribution of corners, edges, and planar faces varies with the size of platinum particles, which is directly related to the reaction conversion and selectivity.
  • the catalyst according to the present invention can be prepared by adjusting the amount of the halogen component to 0.1 to 3.0% by weight relative to the total weight of the catalyst. If the content of halogen is less than 0.1% by weight, the formation of coke on the catalyst is rapidly increased, the coke regeneration of the catalyst is low, the platinum dispersity is low during catalyst regeneration, and if the content of halogen is more than 3.0% by weight, Poisoning of noble metals lowers the activity of the catalyst. That is, the halogen component, in particular chlorine, is combined with the aluminum element of the alumina carrier to attenuate the characteristics of the Lewis acid possessed by the alumina itself, thereby facilitating the desorption of the product, thereby suppressing the formation of coke.
  • the halogen component in particular chlorine
  • the catalyst according to the present invention preferably has a volume density of 0.5 to 0.8 g / cc, and the volume density of the catalyst determines the amount of catalyst charged into the process, which is a factor that determines the total active density of the catalyst introduced into the process. .
  • the catalyst according to the present invention preferably has a strength of 15 to 70 N, and increases the strength so that the catalyst has less rigidity in regeneration or circulation of the catalyst. If the strength of the catalyst is 15N or less, it is easily broken and difficult to apply to the continuous reaction system.
  • the dehydrogenation catalyst is accompanied with the formation of coke, and after a certain reaction, the coke is burned and regenerated through an oxidation reaction, and thermal cracking occurs during the process. In addition, friction and impact are applied during transfer under conditions in which the catalyst is circulated and operated. In the case of using a catalyst that is weak to impact, having a high strength has a great advantage in process operation because it lowers the conversion rate of the catalyst by disturbing the flow of the product and raising the pressure in the reactor.
  • the dehydrogenation catalyst according to the present invention has a macropore size and a high active density of platinum, which is highly active, has a high active density of the unit surface area catalyst, facilitates mass transfer of reactants and products, and results in coke formation. It has the effect of delaying deactivation, high regeneration of coke, and does not change with the initial activity even after regeneration. Its strength is strong against external impact, and there is no structural change or characteristic change of active substance by heat.
  • a catalyst was prepared by a room temperature / temperature adsorption support method. 0.0714 g of tin chloride (SnCl 2 ,> 99%, Sigma), 0.5714 g of hydrochloric acid (HCl,> 35%, JUNSEI) and 0.0714 g of nitric acid (HNO 3 , 70%, Yakuri) were dissolved in 24 g of distilled water, followed by thermal deformation. 20 g of alumina was added and supported.
  • the supporting solution was dried using a rotary evaporator (HAHNSHIN Scientific Co.), stirred at 25 rpm for 1.5 hours at room temperature, and then dried by rotating at 25 rpm for 1.5 hours at 80 ° C under reduced pressure. For complete drying it was dried for 15 hours in a 105 °C oven and heat-treated for 3 hours in a 700 °C heating furnace. Thereafter, 15 g of tin-supported alumina was added to 18.0552 g of distilled water in which 0.3319 g of chloroplatinic acid (H 2 PtCl 6 .6H 2 O, 99.95%, Aldrich), 0.2143 g of hydrochloric acid, and 0.0536 g of nitric acid were dissolved.
  • H 2 PtCl 6 .6H 2 O 0.3319 g of chloroplatinic acid (H 2 PtCl 6 .6H 2 O, 99.95%, Aldrich)
  • the supporting solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, then dried at 25 rpm for 1.5 hours at 80 ° C. under reduced pressure, dried for 15 hours in an oven at 105 ° C., and heated at 600 ° C. Heat treatment for 3 hours in the furnace. Thereafter, 10 g of alumina loaded with tin and platinum was added to 12.1136 g of distilled water in which 0.1933 g of potassium nitrate (KNO 3 ,> 99%, Sigma-Aldrich) and 0.1629 g of hydrochloric acid were dissolved.
  • KNO 3 potassium nitrate
  • the supporting solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, then dried at 25 rpm for 1.5 hours at 80 ° C. under reduced pressure, dried for 15 hours in an oven at 105 ° C., and heated at 600 ° C. Heat treatment for 3 hours in the furnace to prepare a dehydrogenation catalyst.
  • Catalysts A, B and C were obtained by the above preparation method using alumina having different physical properties (specific surface area, pore volume, and strength) shown in Table 1 below.
  • the specific surface area and pore volume of catalysts A, B and C showed a proportional relationship, and the pore volume and the strength of the catalyst showed an inverse relationship.
  • the alumina before the thermal deformation used in the preparation of the catalyst B obtained in Example 1 was thermally deformed for 6 hours at a temperature of 1100 ° C. in a 300 ml / min flow of air using a tubular electric furnace to be used as a catalyst synthesis carrier. It was.
  • the crystallinity of the alumina was measured by X-ray analysis, and the measurement results are shown in FIG. 1 and had more than 90% of theta crystallinity.
  • Catalyst D was obtained by preparing a catalyst in the same manner as in Example 1 using the heat-modified alumina carrier.
  • Catalyst E was prepared by carrying out the heat treatment and the active ingredient in the same manner as in Example 1, except that the carrier in which the macropores were not present in the alumina carrier was used in Example 1.
  • the activity of the catalysts B, D and E prepared in Examples 1 and 2 and Comparative Example 1 is shown in Table 2, and the results of observing the cross sections of the catalysts B, D and E with a scanning electron microscope are shown in FIG. Indicated.
  • Catalyst B Catalyst D
  • Catalyst E Chlorine Content (% by weight) 1.12 0.94 1.15 Mesopore volume (cc / g) 0.47 0.32 0.58 Macro Pore Volume (cc / g) 0.23 0.25 - Strength (N) 31 38 29 Platinum active density (wt% / m2) 0.0036 0.0048 0.0054 Volume density (g / cc) 0.63 0.70 0.59
  • the catalysts B and D have high strength as the macropores are well developed, high platinum activity density per unit area, and high volumetric density of the catalyst.
  • catalyst E has a lower pore volume and lower strength than catalyst B, and no high pore structure was observed inside the catalyst.
  • the catalyst D of the present invention has excellent reaction selectivity due to a high dispersion degree, and has improved propane conversion rate due to a high active density of platinum.
  • the 8-hour average coke production amount of catalysts B, D, and E was 0.328% / hr, 0.251% / hr, and 0.355% / hr, respectively.
  • the active density of the platinum of the catalyst B of the present invention is 0.0036 wt% / m 2 and the platinum of the catalyst E of 0.0054 wt% / m 2 (see Table 2).
  • propane conversion and propylene yield were lower, indicating lower activity.
  • the yield of catalyst E when dehydrogenation was performed at a liquid space velocity of 15 hr ⁇ 1 was lower than the yield of catalyst B when dehydrogenation was performed at a liquid space velocity of 20 hr ⁇ 1 . It is determined that the activity of the catalyst is high due to the size of the macro pores of the catalyst according to the present invention.
  • the dehydrogenation catalyst according to the present invention has a macropore size and a high active density of platinum, which is highly active, has a high active density of the unit surface area catalyst, facilitates mass transfer of reactants and products, and results in coke formation. It has the effect of delaying deactivation, high regeneration of coke, and no change from initial activity even after regeneration, high strength, strong against external impact, no structural change by heat or characteristic change of active substance.

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Abstract

본 발명은 탄화수소 기체의 탈수소화 반응에 사용되는, 매크로 기공의 크기를 가지며 백금의 높은 활성밀도를 갖는 탈수소화 촉매에 관한 것이다. 본 발명에 따른 탈수소화 촉매는 매크로 기공의 크기를 갖고, 백금의 높은 활성밀도를 가짐으로써, 고활성이며, 단위표면적 촉매의 활성밀도가 높고, 반응물과 생성물의 물질 전달이 용이하며, 코크 생성에 따른 비활성화가 지연되는 효과가 있고, 코크 재생성이 높아 재생 후에도 초기의 활성과 변함이 없으며, 강도가 높아 외적 충격에 강하고, 열에 의한 구조적 변화나 활성 물질의 특성 변화가 없다.

Description

탈수소화 촉매
본 발명은 탄화수소 기체의 탈수소화 반응에 사용되는, 매크로 기공의 크기를 가지며 백금의 높은 활성밀도를 갖는 탈수소화 촉매에 관한 것이다.
탄화수소 기체의 탈수소화 반응은 550℃ 이상의 고온에서 진행된다. 촉매 반응이 고온에서 진행됨에 따라, 그에 대한 부반응으로 열분해 및 코크 생성반응이 수반되고, 이러한 부반응의 정도가 촉매의 선택도 및 활성을 결정짓는 핵심 요소가 된다. 부반응의 하나인 코크 생성 반응은 촉매상의 활성물질을 코크로 덮이게 하여 반응물과 접촉을 차단시킴으로써 전반적인 반응전환율을 낮추게 된다. 또한, 코크의 생성이 진행됨에 따라 촉매 내에 존재하는 기공의 입구를 막아 기공 내에 존재하는 활성물질을 무용화하여 급격하게 비활성화를 촉진한다.
탄화수소의 탈수소화 촉매의 또 다른 요구사항으로는 열적 안정성을 들 수 있다. 고온의 반응온도와 촉매의 코크재생 과정에서 발생하는 열에 의해 촉매 자체의 열적 변형 및 구조적 소결 현상을 가져오고, 그에 따른 촉매 반응성의 변화를 야기한다. 상기의 이유로 인해 촉매의 구조적 적합성, 촉매 구조의 열적 안정성, 활성 성분의 열적 안정성, 촉매의 코크 재생성은 우수한 촉매를 결정짓는 주요 요소가 된다.
일반적으로, 탈수소화 촉매는 크롬 산화물 촉매와 백금 촉매의 두 부류로 나뉜다.
크롬계 촉매(미국특허 제 6,797,850호)는 코크 생성에 따른 촉매의 비활성화 속도가 빠르며, 그에 따른 재생 속도가 빠르기 때문에 촉매의 수명이 백금계 촉매에 비해 짧은 편이고, 크롬 자체의 독성으로 인한 문제를 내재하고 있다.
백금계 촉매 중에는, 40~160㎛의 활성성분이 함유된 외부층을 갖는 촉매가 있으며, 내부에는 감마-알루미나(미국특허 제 6,756,515호) 또는 알파-알루미나(미국특허 제 6,486,370호)를 기반으로 각각의 층을 이루는 형태의 촉매가 있으나, 기공에 의한 촉매의 비표면적을 결정짓는 내부층에는 금속 활성성분이 존재하지 않게 되어 낮은 분산도 및 낮은 활성면적을 갖는 특성을 지닐 수 있게 된다. 또한, 감마-알루미나의 사용은 알루미나 자체의 산점으로 인한 부반응성이 크고, 반응중 알루미나 결정성이 변화하고 비표면적이 감소하는 구조적 특성 변화를 가져오게 되며, 알파-알루미나는 낮은 비표면적으로 인해 귀금속의 분산도를 낮추고 전체적인 귀금속의 활성면적을 감소시켜 낮은 촉매활성을 나타낸다.
촉매의 제조에 있어, 염소 성분이 제거된 형태의 백금계 촉매를 제조하여 에탄의 탈수소화에 적용한 형태(미국특허 제 7,375,049호)가 있으나, 염소가 없는 경우 반응 초기의 활성이 높을 수 있으나, 공정 내에서 장기 사용할 경우 활성금속 성분의 뭉침현상(sintering)이 진행되어 분산도가 낮아지고 결국에는 활성이 저하되는 특성을 갖게 된다(Catalysis Today 111 (2006) 133-139).
촉매의 담체로는 실리카(미국특허 제 7,432,406호), 제올라이트나 보론실리케이트(미국특허 제 6,555,724호)를 사용하여 백금계 촉매를 제조하기도 하나, 이들 촉매는 기본적으로 평균 기공 직경이 10㎚ 이하인 기공이 주를 이루며, 이로 인해 코크 생성에 따른 구조적 폐쇄에 매우 민감하게 작용하게 되어, 촉매의 비활성화가 급격히 진행될 수 있다.
종래에 공지된 탈수소화 촉매 관련 특허에는 촉매의 활성성분 및 담체의 종류에 대한 내용이 주류를 이루며, 촉매의 물리적 특징의 하나인 기공분포도에 대한 내용은 아직까지 전무한 상태이다. 기공의 부피와 기공의 크기는 반응물과 생성물의 물질 전달 계수를 결정짓는 주요 인자이며, 화학반응 속도가 빠른 상황에서 물질의 확산 저항은 전체적인 반응속도를 결정짓기 때문에 기공의 크기가 큰 구조체가 촉매의 활성을 높게 유지하는데 유리할 수 있으며, 기공의 크기가 큰 담체를 사용하는 것이 코크의 축적에 둔감하게 작용하여 촉매활성 유지에 유리할 수 있다.
따라서, 매크로 기공의 크기를 가지며, 촉매의 활성, 선택성 및 코크 안정이 우수한 탈수소화 촉매의 개발이 요구되고 있다.
본 발명자들은 매크로 기공의 크기를 가지며, 촉매의 활성, 선택성 및 코크 안정이 우수한 탈수소화 촉매에 대해 연구하던 중, 매크로 기공의 크기를 가지며, 백금의 높은 활성밀도를 갖는 탈수소화 촉매를 열변형된 알루미나 담체를 사용하여 상온/승온 흡착 담지법으로 제조하였으며, 상기 제조된 촉매를 이용하여 프로판을 탈수소 반응을 수행한 결과 전환율, 선택도 및 수율이 높게 나타남을 확인하고, 본 발명을 완성하였다.
본 발명은 탄화수소 기체의 탈수소화 반응에 사용되는, 매크로 기공의 크기를 가지며 백금의 높은 활성밀도를 갖는 탈수소화 촉매를 제공하고자 한다.
도 1은 본 발명에 따른 촉매 B와 D의 알루미나의 결정성을 X-ray 분석법을 이용하여 측정한 결과를 나타낸 도이다.
도 2는 본 발명에 따른 촉매 B와 D의 단면을 주사전자현미경으로 관찰한 도이다.
도 3은 본 발명에 따른 촉매 B와 D를 이용하여 프로판을 탈수소 반응시킨 후 기체 크로마토그래피로 분석하여 프로판 전환율과 반응 후 생성물 중의 프로필렌 선택도를 나타낸 도이다.
본 발명은 탄화수소 기체의 탈수소화 반응에 사용되는 촉매에 있어서, 백금, 보조금속, 알칼리 금속 또는 알칼리토금속, 및 할로겐 성분이 담체에 담지된 형태를 가지며, 상기 담체는 5~100㎚의 메조 기공과 0.1~20㎛의 매크로 기공을 갖고, 백금의 활성밀도는 0.001~0.009 중량%/㎡인 것을 특징으로 하는 탈수소화 촉매를 제공한다.
상기 탄화수소는 C2~C5의 선형 탄화수소 또는 에틸벤젠이다.
이하, 본 발명에 대해 상세히 설명한다.
본 발명에 따른 탈수소화 촉매는 촉매 총 중량에 대해 백금 0.05~1.5 중량%, 보조금속 0.05~2.0 중량%, 알칼리 금속 또는 알칼리토금속 0.05~3.0 중량%, 및 할로겐 성분 0.1~3.0 중량%를 담체에 담지시켜 상온/승온 흡착 담지법으로 제조한다.
상기 백금은 주요금속으로 사용되며, 보조금속으로는 주석, 게르마늄, 갈륨, 인듐, 아연 및 망간으로 이루어진 군으로부터 선택된 것을 사용하며, 특히 주석이 바람직하다. 알칼리 금속 또는 알칼리토금속은 칼슘, 칼륨, 나트륨, 마그네슘, 리튬, 스트론튬, 바륨, 라듐 및 베릴륨으로 이루어진 군으로부터 선택된 것을 사용한다. 할로겐 성분으로는 염소, 인 및 불소로 이루어진 군으로부터 선택된 것을 사용하며, 특히 염소가 바람직하다.
본 발명에 따른 촉매에서, 담체는 알루미나, 실리카 및 이의 혼합성분이 사용될 수 있으며, 바람직하게는 알루미나가 적당하다. 알루미나의 세타 결정성은 코크의 생성 정도를 결정해주는 인자로서, 90% 이상이 바람직하다.
상기 담체는 비표면적이 50~170㎡/g이고, 5~100㎚의 메조 기공과 0.1~20㎛의 매크로 기공을 갖는다. 만일 담체의 비표면적이 50㎡/g 미만이면 금속 활성 성분의 분산도가 낮아지고, 170㎡/g을 초과하면 알루미나의 감마 결정성이 높게 유지되어 부반응성이 증대된다. 또한, 담체 기공의 부피와 기공의 크기는 반응물과 생성물의 물질 전달 계수를 결정짓는 주요 인자이며, 화학반응 속도가 빠른 상황에서 물질의 확산 저항은 전체적인 반응속도를 결정짓기 때문에 기공의 크기가 큰 구조체가 촉매의 활성을 높게 유지하는데 유리하다. 따라서, 기공의 크기가 큰 담체를 사용하는 것이 코크의 축적에 둔감하게 되고, 물질 전달 속도가 높아 액체공간속도 (liquid hourly space velocity; LHSV)의 증가에도 높은 반응 활성을 보이게 된다. 담체의 기공이 5㎚ 미만이면 누슨 확산(Knudsen diffusion)에 의해 물질전달 속도가 떨어지고, 담체의 기공이 20㎛를 초과하면 담체의 강도가 떨어지게 된다. 즉, 기공의 크기가 10㎚ 이하에서는 누슨 확산, 10~1000㎚에서는 전이확산(transition diffusion), 1000㎚ 이상에서는 체적확산(bulk diffusion)을 갖기 때문에 1㎛ 이상의 매크로 기공을 갖는 것은 10㎚의 기공에 비해 20배 이상의 물질전달 속도를 갖는다("Heterogeneous Catalysis In Practice" Charles N. Satterfield, p.334-344 (1980, McGraw-Hill)).
본 발명에 따른 탈수소화 촉매는 백금의 높은 분산도를 갖는 촉매로서, 활성점으로 작용되는 백금의 활성밀도는 0.001~0.009 중량%/㎡가 바람직하다. 만일 백금의 활성밀도가 0.001 중량%/㎡ 미만이면 활성점이 충분하지 못해 반응 전환율이 낮아지게 되고, 0.009 중량%/㎡를 초과하면 백금의 분산도가 낮아져 코크의 생성량이 증대하고 부반응성이 높아져 반응 선택도가 낮아지게 된다. 백금의 활성밀도는 입자의 크기를 결정짓는 핵심 요소이다. 백금 입자의 크기에 따라 corner, edge, planar face의 분포도가 변하게 되는데, 이는 반응 전환율 및 선택도와 직접적인 관련을 갖는다. 백금의 입자가 1.35㎚인 경우 corner가 50% 존재하는 반면, 입자의 크기가 2.15㎚가 되면 corner가 18%, edge가 45%, plane face가 37%로 되며, 입자의 크기가 5.1㎚가 되면 corner가 3%, edge가 27%, plane face가 70% 정도로 그 특성이 변하게 되어 촉매반응에서 전환율과 선택도의 변화를 가져온다("Catalyst Preparation", John Regalbuto, p.422-448 (2006, CRC Press)).
본 발명에 따른 촉매는 할로겐 성분의 양을 촉매 총 중량에 대해 0.1~3.0 중량%로 조절하여 제조할 수 있다. 만일 할로겐의 함량이 0.1 중량% 미만이면 촉매상에 코크의 생성속도가 급격히 높아지고 촉매의 코크 재생성이 낮아지며 촉매 재생시 백금의 분산도가 낮아지고, 할로겐의 함량이 3.0 중량%를 초과하면 할로겐에 의한 귀금속의 피독현상으로 촉매의 활성이 낮아지게 된다. 즉, 할로겐 성분, 특히 염소는 알루미나 담체의 알루미늄 원소와 결합되어 알루미나 자체가 갖고 있는 루이스 산의 특성을 감쇠시켜 생성물의 탈착을 용이하게 하며, 그로 인한 코크의 생성을 억제하는 효과를 갖는다. 코크의 생성은 담체 자체에서 흡착하며 반응이 완결되거나, 활성점에서 생성된 주산물/부산물이 스필-오버(spill-over) 되어 담체에 적체되고 추가적인 코크 생성 반응을 통해 최종적으로 생성되기도 하지만, 루이스 산을 약화시켜 생성물의 탈착을 용이하게 하면 담체에 적체되는 양이 줄어들어 코크 생성을 감소시킬 수 있다. 또한, 알루미나의 결정성 자체에 내재된 산점을 감소시키는 방향으로, 감마의 성상에서 세타 또는 알파의 성상으로 변형 시킴으로써도 동일한 산점 감소의 효과를 보이게 된다. 또, 촉매의 재생 과정 중에 백금의 소결현상을 제어하기 위해서도 염소가 활용된다("Reactivation of sintered Pt/Al2O3 oxidation catalysts" F. Cabello Galisteo et al., Appl. Catal. B 59 (2005) 227-233).
본 발명에 따른 촉매는 0.5~0.8g/cc의 체적밀도를 갖는 것이 바람직하며, 촉매의 체적밀도는 공정내 투입되는 촉매의 충진량을 결정짓게 되어 공정 내에 투입된 촉매의 총 활성밀도를 결정짓는 인자이다.
본 발명에 따른 촉매는 15~70N의 강도를 갖는 것이 바람직하며, 강도를 높여 재생이나 촉매의 순환에도 부스러짐이 적은 강성을 갖도록 한다. 만일 촉매의 강도가 15N 이하이면 쉽게 깨어져 연속식 반응시스템에 적용하기 어렵게 된다. 탈수소화 촉매는 코크 생성이 수반되어 일정 반응 후에는 산화 반응을 통해 코크를 태워 재생하게 되는데, 그 공정 중에 열적 깨짐 현상이 발생한다. 또한, 촉매를 순환시키며 운전하는 조건에서는 이송 중에 마찰이나 충격이 가해지게 된다. 충격에 약한 촉매를 사용하는 경우, 생성물의 흐름을 방해하고 반응기 내의 압력을 상승시켜 촉매의 전환율을 낮추기 때문에 높은 강도를 갖는 것이 공정 운전상에 커다란 잇점을 주게 된다.
본 발명에 따른 탈수소화 촉매는 매크로 기공의 크기를 가지며 백금의 높은 활성밀도를 가짐으로써, 고활성이며, 단위표면적 촉매의 활성밀도가 높고, 반응물과 생성물의 물질 전달이 용이하며, 코크 생성에 따른 비활성화가 지연되는 효과가 있고, 코크 재생성이 높아 재생 후에도 초기의 활성과 변함이 없으며, 강도가 높아 외적 충격에 강하고, 열에 의한 구조적 변화나 활성 물질의 특성 변화가 없다.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.
실시예 1 : 탈수소화 촉매의 제조
미국특허 제 4,542,113호에 준하여 제조된 구형의 감마 결정성을 갖는 알루미나를 독일의 사솔(Sasol)사에서 구입하여, 관형의 전기로(고려전기로)를 이용하여 공기의 흐름 300㎖/min 상에서 1050℃의 온도로 6시간 동안 열변형하여 촉매합성의 담체로 사용하였다. X-ray 분석법을 이용하여 알루미나의 결정성을 측정하였으며, 측정 결과는 도 1에 나타내었고, 90% 이상의 세타 결정성을 가지고 있었다.
상기 열변형된 알루미나 담체를 사용하여 상온/승온 흡착 담지법으로 촉매를 제조하였다. 주석 염화물(SnCl2, >99%, Sigma) 0.0717g, 염산(HCl, >35%, JUNSEI) 0.5714g, 질산(HNO3, 70%, Yakuri) 0.0714g을 증류수 24g에 넣어 녹인 후, 열변형된 알루미나 20g을 넣어 담지하였다. 담지액은 회전증발기(HAHNSHIN Scientific Co.)를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 감압 상태 80℃에서 1.5시간 동안 25rpm으로 회전시켜 건조하였다. 완전한 건조를 위하여 105℃ 오븐에서 15시간 동안 건조하고, 700℃ 가열로에서 3시간 동안 열처리하였다. 이후, 주석이 담지된 알루미나 15g을 염화 백금산(H2PtCl6·6H2O, 99.95%, Aldrich) 0.3319g, 염산 0.2143g, 질산 0.0536g이 녹아있는 증류수 18.0552g에 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 감압 상태 80℃에서 1.5시간 동안 25rpm으로 회전시켜 건조하였고, 105℃ 오븐에서 15시간 동안 건조하고, 600℃ 가열로에서 3시간 동안 열처리하였다. 이후, 주석과 백금이 담지된 알루미나 10g을 질산 칼륨(KNO3, >99%, Sigma-Aldrich) 0.1933g, 염산 0.1629g이 녹아있는 증류수 12.1136g에 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 감압 상태 80℃에서 1.5시간 동안 25rpm으로 회전시켜 건조하였고, 105℃ 오븐에서 15시간 동안 건조하고, 600℃ 가열로에서 3시간 동안 열처리하여 탈수소화 촉매를 제조하였다.
하기 표 1에 나타낸 물리적 물성(비표면적, 기공부피, 강도)이 서로 다른 알루미나를 이용하여 상기의 제조법으로 촉매 A, B 및 C를 얻었다. 촉매 A, B 및 C의 비표면적과 기공부피는 비례관계의 특성을 나타내었고, 기공부피와 촉매의 강도는 반비례 관계의 특성을 나타내었다.
표 1 알루미나 담체의 물리적 성질(비표면적, 기공부피, 강도)
담체 촉매 A 촉매 B 촉매 C
비표면적(㎡/g) 96 124 150
기공부피(cc/g) 0.34 0.70 0.86
강도(N) 48 31 15
실시예 2 : 탈수소화 촉매의 제조
상기 실시예 1에서 얻은 촉매 B의 제조에 활용된 열변형 전의 알루미나를, 관형의 전기로를 이용하여 공기의 흐름 300㎖/min 상에서 1100℃의 온도로 6시간 동안 열변형하여 촉매합성의 담체로 사용하였다. X-ray 분석법을 이용하여 알루미나의 결정성을 측정하였으며, 측정 결과는 도 1에 나타내었고, 90% 이상의 세타 결정성을 가지고 있었다.
상기 열변형된 알루미나 담체를 사용하여 실시예 1과 동일한 방법으로 촉매를 제조하여 촉매 D를 얻었다.
비교예 1 : 매크로 기공이 존재하지 않는 담체를 사용하여 탈수소화 촉매의 제조
상기 실시예 1에서 알루미나 담체 내에 매크로 기공이 존재하지 않는 담체를 사용한 것을 제외하고는, 실시예 1과 동일하게 열처리 및 활성성분을 담지하여 촉매 E를 제조하였다.
실험예 1 : 탈수소화 촉매의 활성 평가
상기 실시예 1~2 및 비교예 1에서 제조한 촉매 B, D 및 E의 활성을 평가하여 표 2에 나타내었으며, 촉매 B, D 및 E의 단면을 주사전자현미경으로 관찰한 결과는 도 2에 나타내었다.
표 2
. 촉매 B 촉매 D 촉매 E
염소 함량(중량%) 1.12 0.94 1.15
메조기공 부피(cc/g) 0.47 0.32 0.58
매크로기공 부피(cc/g) 0.23 0.25 -
강도(N) 31 38 29
백금 활성밀도(중량%/㎡) 0.0036 0.0048 0.0054
체적밀도(g/cc) 0.63 0.70 0.59
표 2 및 도 2에 나타난 바와 같이, 촉매 B와 D는 매크로 기공이 잘 발달되면서 높은 강도를 가지며, 단위 면적당 백금 활성밀도가 높고, 촉매의 체적밀도가 높은 특징을 보였다. 반면, 촉매 E는 촉매 B에 비해 기공의 부피가 낮고 강도가 낮으며, 촉매 내부에 고기공 구조는 관찰되지 않았다.
실험예 2 : 탈수소화 촉매의 성능 실험
본 발명에 따른 탈수소화 촉매의 성능을 확인하기 위하여, 하기와 같은 실험을 수행하였다.
상기 실시예 1 및 2에서 제조된 촉매 B, D 및 E 3.2㎖를 부피가 7㎖인 석영반응기 내에 각각 충진한 후, 프로판과 수소의 혼합기체를 공급하여 탈수소 반응을 각각 수행하였다. 이때, 수소와 프로판의 비율은 1:1로 고정하였으며, 단열조건 하에서 반응온도는 620℃, 절대압력은 1.5atm, 액체공간속도는 15hr-1로 유지하면서 탈수소 반응을 수행하였다. 반응 후의 기체 조성은 반응 장치와 연결된 기체 크로마토그래피로 분석하여 프로판 전환율과 반응 후 생성물 중의 프로필렌 선택도를 구하였다.
결과는 도 3에 나타내었다.
도 3에 나타난 바와 같이, 본 발명의 촉매 D는 높은 분산도의 특징으로 반응 선택도가 우수하고, 백금의 활성밀도가 높아진 특징으로 인해 프로판 전환율을 향상시켰다. 또한, 촉매 B, D 및 E의 8시간 평균 코크의 생성량은 각각 0.328%/hr, 0.251%/hr 및 0.355%/hr이었다.
실험예 3 : 액체공간속도와 백금의 활성밀도의 차이에 따른 탈수소화 촉매의 성능 실험
상기 실험예 2에서 촉매 B를 이용하여 액체공간속도를 10hr-1 및 20hr-1로 유지한 것을 제외하고는, 실험예 2와 동일하게 하여 탈수소 반응을 수행하였다. 반응 후의 기체 조성은 반응 장치와 연결된 기체 크로마토그래피로 분석하여 프로판 전환율과 프로필렌 수율을 구하였다.
결과는 표 3에 나타내었다.
표 3
. 반응시간
1시간 5시간 10시간 20시간
액체공간속도(LHSV) 전환율(중량%) 수율(중량%) 전환율(중량%) 수율(중량%) 전환율(중량%) 수율(중량%) 전환율(중량%) 수율(중량%)
촉매 E(15hr-1) 31.8 30.4 29.6 28.3 28.2 27.0 26.6 25.4
촉매 B(10hr-1) 39.9 36.3 37.9 35.1 36.7 34.2 35.1 32.8
촉매 B(20hr-1) 36.4 34.2 34.2 32.5 32.4 30.9 30.3 29.0
표 3에 나타난 바와 같이, 본 발명의 촉매 B의 백금의 활성밀도가 0.0036 중량%/㎡이고 촉매 E의 백금의 활성밀도가 0.0054 중량%/㎡로(표 2 참조), 촉매 E의 백금의 활성밀도가 더 높음에도 불구하고 프로판 전환율과 프로필렌 수율이 낮게 나타나 낮은 활성을 보였다. 또한, 액체공간속도를 15hr-1 하여 탈수소 반응하였을 때의 촉매 E의 수율은 액체공간속도를 20hr-1 하여 탈수소 반응하였을 때의 촉매 B의 수율보다도 낮게 나타났다. 이는, 본 발명에 따른 촉매의 매크로 기공의 크기 때문에 촉매의 활성이 높게 나타나는 것으로 판단된다.
본 발명에 따른 탈수소화 촉매는 매크로 기공의 크기를 가지며 백금의 높은 활성밀도를 가짐으로써, 고활성이며, 단위표면적 촉매의 활성밀도가 높고, 반응물과 생성물의 물질 전달이 용이하며, 코크 생성에 따른 비활성화가 지연되는 효과가 있고, 코크 재생성이 높아 재생 후에도 초기의 활성과 변함이 없으며, 강도가 높아 외적 충격에 강하고, 열에 의한 구조적 변화나 활성 물질의 특성 변화가 없다.

Claims (11)

  1. 탄화수소 기체의 탈수소화 반응에 사용되는 촉매에 있어서, 백금, 보조금속, 알칼리 금속 또는 알칼리토금속, 및 할로겐 성분이 담체에 담지된 형태를 가지며, 상기 담체는 5~100㎚의 메조 기공과 0.1~20㎛의 매크로 기공을 갖고, 백금의 활성밀도는 0.001~0.009 중량%/㎡인 것을 특징으로 하는 탈수소화 촉매.
  2. 제 1항에 있어서, 상기 탄화수소는 C2~C5의 선형 탄화수소 또는 에틸벤젠인 것을 특징으로 하는 탈수소화 촉매.
  3. 제 1항에 있어서, 상기 촉매는 촉매 총 중량에 대해 백금 0.05~1.5 중량%, 보조금속 0.05~2.0 중량%, 알칼리 금속 또는 알칼리토금속 0.05~3.0 중량%, 및 할로겐 성분 0.1~3.0 중량%를 담체에 담지시킨 형태인 것을 특징으로 하는 탈수소화 촉매.
  4. 제 1항에 있어서, 상기 보조금속은 주석, 게르마늄, 갈륨, 인듐, 아연 및 망간으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 탈수소화 촉매.
  5. 제 1항에 있어서, 상기 알칼리 금속 또는 알칼리토금속은 칼슘, 칼륨, 나트륨, 마그네슘, 리튬, 스트론튬, 바륨, 라듐 및 베릴륨으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 탈수소화 촉매.
  6. 제 1항에 있어서, 상기 할로겐 성분은 염소, 인 및 불소로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 탈수소화 촉매.
  7. 제 1항에 있어서, 상기 담체는 알루미나, 실리카 및 이의 혼합성분으로 이루어진 군으로부터 선택된 것임을 특징으로 하는 탈수소화 촉매.
  8. 제 7항에 있어서, 상기 알루미나는 90% 이상의 세타 결정성을 갖는 것을 특징으로 하는 탈수소화 촉매.
  9. 제 1항에 있어서, 상기 담체는 비표면적이 50~170㎡/g인 것을 특징으로 하는 탈수소화 촉매.
  10. 제 1항에 있어서, 상기 촉매는 0.5~0.8g/cc의 체적밀도를 갖는 것을 특징으로 하는 탈수소화 촉매.
  11. 제 1항에 있어서, 상기 촉매는 15~70N의 강도를 갖는 것을 특징으로 하는 탈수소화 촉매.
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US8993474B2 (en) 2015-03-31
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ES2388863B2 (es) 2013-08-06
KR20100078465A (ko) 2010-07-08
MY161877A (en) 2017-05-15
CN102271806A (zh) 2011-12-07
US20110263416A1 (en) 2011-10-27

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