KR20110062968A - Preparation of cobalt and/or nickel-molybdenum sulfide sulfide catalyst supported on alumina for deep hydrodesulfurization - Google Patents
Preparation of cobalt and/or nickel-molybdenum sulfide sulfide catalyst supported on alumina for deep hydrodesulfurization Download PDFInfo
- Publication number
- KR20110062968A KR20110062968A KR1020090119870A KR20090119870A KR20110062968A KR 20110062968 A KR20110062968 A KR 20110062968A KR 1020090119870 A KR1020090119870 A KR 1020090119870A KR 20090119870 A KR20090119870 A KR 20090119870A KR 20110062968 A KR20110062968 A KR 20110062968A
- Authority
- KR
- South Korea
- Prior art keywords
- cobalt
- alumina
- nickel
- molybdenum sulfide
- catalyst
- Prior art date
Links
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/20—Sulfiding
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
Abstract
Description
본 발명은 심도탈황용 알루미나 담지 몰리브덴 황화물 촉매의 제조방법에 관한 것으로, 보다 상세하게는, 초음파를 이용하여 주촉매인 몰리브덴 황화물을 알루미나에 고분산시켜 담지시키고, 조촉매인 코발트 및/또는 니켈 전구체를 몰리브덴 황화물에 담지 시킴으로써 우수한 활성을 갖는 심도탈황용 알루미나 담지 코발트 및/또는 니켈-몰리브덴 황화물 촉매를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing an alumina-supported molybdenum sulfide catalyst for deep desulfurization, and more particularly, to a high dispersion of the molybdenum sulfide as a main catalyst to alumina by using ultrasonic waves, and cobalt and / or nickel precursor as a promoter The present invention relates to a method for producing an alumina-supported cobalt and / or nickel-molybdenum sulfide catalyst for deep desulfurization having an excellent activity by supporting a molybdenum sulfide.
종래의 탈황공정에서 황 함량을 낮추기 위해서는 고온, 고압의 가혹한 운전조건에서 운전해야 하므로 운전비용이 증가하고, 촉매의 수명이 단축되는 등의 문제점이 있다. In order to lower the sulfur content in the conventional desulfurization process, it is necessary to operate in harsh operating conditions of high temperature and high pressure, thereby increasing operating costs and shortening the life of the catalyst.
현재 심도 탈황용 촉매 기술로써 미국특허 제3,509,044호 및 제3,674,680호에는 감마 알루미나를 몰리브덴 및 코발트 전구체 수용액에 함침하여 몰리브덴 및 코발트 전구체를 담지시킨 후, 건조, 소성 및 황화 과정을 통해 제조하는 방법이 개시되어 있다. US Patent Nos. 3,509,044 and 3,674,680 disclose a method for preparing molybdenum and cobalt precursors by impregnating gamma alumina in an aqueous solution of molybdenum and cobalt precursors, followed by drying, calcining and sulfiding. It is.
미국특허 제4,568,449호 및 제5,514,274호에는 탈황촉매의 성능을 개선하기 위하여 산성물질인 인을 첨가하여 활성을 증진시킨 예가 기재되어 있다. 그러나 고온의 열처리 과정에서 코발트 및 몰리브덴의 소결현상이 일어나기 때문에 금속의 분산도가 감소되어 활성이 증가되는 정도가 미미하다는 한계가 있다. US Pat. Nos. 4,568,449 and 5,514,274 describe examples of enhancing the activity by adding phosphoric acid, an acidic substance, to improve the performance of a desulfurization catalyst. However, since the sintering phenomenon of cobalt and molybdenum occurs during the high temperature heat treatment process, there is a limit that the degree of activity increase is insignificant due to the decrease in metal dispersion.
미국특허 제4,243,554호 및 제6,156,693호에는 탈황촉매에 존재하는 금속 활성상의 표면적을 증가시키기 위하여 암모늄테트라티오몰리브데이트를 전구체로 사용한 예가 개시되어 있다. 그러나 이 방법에 의하면 암모늄테트라티오몰리브데이트가 저온에서 분해되므로 저온에서 촉매를 제조할 수 있으나, 근본적으로 무담지 상태의 촉매 제조방법에 관한 것으로, 위 방법에 의해 제조된 촉매는 알루미나 담지 촉매를 사용하는 기존의 탈황공정에서 사용하기는 어렵다. US Pat. Nos. 4,243,554 and 6,156,693 disclose examples of using ammonium tetrathiomolybdate as a precursor to increase the surface area of the metal active phase present in the desulfurization catalyst. However, according to this method, since ammonium tetrathiomolybdate is decomposed at a low temperature, a catalyst can be prepared at a low temperature. However, the catalyst prepared by the above method is an alumina supported catalyst. It is difficult to use in the existing desulfurization process.
한국공개특허 제2003-0047416호에는 초음파를 이용하여 알루미나 담체위에 몰리브덴 황화물 입자를 고분산도로 담지시키는 촉매의 제조방법이 개시되어 있는데 이 방법으로 제조된 촉매는 조촉매인 코발트 및/또는 니켈을 포함하고 있지 않기 때문에 기존의 코발트 및/또는 니켈-몰리브덴 황화물 촉매에 비하여 활성이 낮다는 문제점이 있다.Korean Patent Laid-Open Publication No. 2003-0047416 discloses a method for preparing a catalyst for supporting molybdenum sulfide particles on alumina carrier with high dispersion by using ultrasonic waves. The catalyst prepared by this method includes cobalt and / or nickel as a promoter. There is a problem in that the activity is lower than the conventional cobalt and / or nickel- molybdenum sulfide catalyst because it is not.
한국공개특허 제2006-0020151호에는 초음파를 이용하여 알루미나 담체 위에 몰리브덴 황화물 입자를 고분산도로 담지 시킨 후 코발트 전구체를 화학 증착하여 고활성 촉매를 제조하는 내용이 개시되어 있으나, 코발트를 화학 증착하는 과정에서 코발트 전구체 손실이 매우 크다. 또한 전구체를 기화시켜 기체 상태로 담지하는 방법이므로 촉매 제법을 실제 상업 촉매 제조 공정에 적용하기 어려운 문제점이 있다.Korean Laid-Open Patent Publication No. 2006-0020151 discloses a method of preparing a highly active catalyst by chemically depositing a cobalt precursor after supporting molybdenum sulfide particles on an alumina carrier by using ultrasonic waves, and cobalt is chemically deposited. The cobalt precursor loss is very large at. In addition, since the precursor is vaporized and supported in a gaseous state, there is a problem in that the catalyst preparation method is difficult to apply to an actual commercial catalyst manufacturing process.
상기한 문제점을 극복하기 위해 본 발명은 심도 탈황용 촉매의 활성상인 코발트및/또는 니켈-몰리브덴 황화물을 알루미나 담체 위에 고분산시켜 담지함으로써 높은 활성을 가진 심도 탈황용 알루미나 담지 코발트 및/또는 니켈-몰리브덴 황화물 촉매의 제조방법을 제공하고자 한다. In order to overcome the above problems, the present invention provides cobalt and / or nickel-molybdenum for deep desulfurization having high activity by carrying out high dispersion of cobalt and / or nickel-molybdenum sulfide, which is an active phase of a catalyst for depth desulfurization, on an alumina carrier. It is intended to provide a method for preparing a sulfide catalyst.
상기한 목적을 달성하기 위해, 본 발명의 일 측면은 (A) 유기용매에 황을 용해시키고, 황-유기용매 용액에 몰리브덴 헥사카르보닐과 감마 알루미나를 투입한 후, 초음파를 가하여 알루미나에 몰리브덴 황화물을 담지 시키는 단계, (B) 상기 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나에 조촉매인 코발트 및/또는 니켈 전구체를 용매에 녹여 함침하고 400℃ 미만 온도에서 열처리하여 코발트 및/또는 니켈-몰리브덴 황화물 촉매를 제조하는 단계; 및 (C) 고압의 수소 내에서, 상기 (B) 단계에서 제조된 코발트 및/또는 니켈 몰리브덴 황화물이 담지된 알루미나를 황화제와 반응시켜 코발트 및/또는 니켈을 황화시키는 단계를 포함하는 심도탈황용 알루미나 담지 몰리브덴 황화물 촉매의 제조방법을 제공한다. In order to achieve the above object, one aspect of the present invention is (A) dissolving sulfur in an organic solvent, molybdenum hexacarbonyl and gamma alumina are added to a sulfur-organic solvent solution, and then ultrasonically added to molybdenum sulfide in alumina (B) impregnating cobalt and / or nickel precursors as cocatalysts in alumina loaded with molybdenum sulfide prepared in step (A) in a solvent and heat-treating at a temperature below 400 ° C. to cobalt and / or nickel. Preparing a molybdenum sulfide catalyst; And (C) sulphurizing cobalt and / or nickel by reacting alumina loaded with cobalt and / or nickel molybdenum sulfide prepared in step (B) with a sulfiding agent in hydrogen at high pressure. Provided is a method for producing an alumina supported molybdenum sulfide catalyst.
본 발명의 발명자는 코발트 및/또는 니켈 전구체를 함침법으로 도입하는 방법을 사용하여, 화학증착법에 사용하는 코발트 전구체인 코발트트리카르보닐니트로실보다 훨씬 저렴한 코발트 및/또는 니켈아세틸아세토네이트 전구체를 사용하였으며, 공정또한 상업적용이 용이한 함침법으로 촉매에 담지하여 코발트 전구체의 손 실이 없고 탈황성능이 우수한 촉매를 제조하는 방법을 개발할 수 있었다. The inventor of the present invention uses a method of introducing cobalt and / or nickel precursors by impregnation, and uses cobalt and / or nickel acetylacetonate precursors which are much cheaper than cobalt tricarbonylnitrosyl, which is a cobalt precursor used in chemical vapor deposition. In addition, the process was also supported by the impregnation method for easy commercial use to develop a method for producing a catalyst having excellent desulfurization performance without loss of cobalt precursor.
이하, 각 단계별로 보다 상세하게 설명한다. Hereinafter, each step will be described in more detail.
(A) 단계는 크게 유기용매에 황을 녹이는 공정과 황-유기용매 용액 내에서 감마 알루미나에 몰리브덴 전구체를 담지시키는 공정으로 구분된다.Step (A) is largely divided into a process of dissolving sulfur in an organic solvent and a process of supporting a molybdenum precursor in gamma alumina in a sulfur-organic solvent solution.
유기용매에 황을 녹이는 공정은, 반응기에 아르곤을 흘려주면서 초음파를 가하여 효과적으로 수행할 수 있다. 바람직하게는 20-40kHz, 50-100W/cm2의 초음파를 가한다.The process of dissolving sulfur in the organic solvent can be effectively performed by applying ultrasonic waves while flowing argon to the reactor. Preferably 20-40 kHz, 50-100 W / cm 2 ultrasonic waves are added.
사용 유기용매에는 몰리브덴 전구체와 황을 녹이는 용매로써, 헥사데칸, 1,2,3,5-테트라메틸벤젠, 1,3,5-트리메틸벤젠 또는 이들의 혼합물을 사용하는 것이 바람직하나 이로 한정하는 것은 아니다. In the organic solvent used, hexadecane, 1,2,3,5-tetramethylbenzene, 1,3,5-trimethylbenzene, or a mixture thereof is preferably used as a solvent for dissolving molybdenum precursor and sulfur. no.
감마 알루미나에 몰리브덴 전구체를 담지시키는 공정은 황-유기용매 용액에 감마 알루미나와 몰리브덴 전구체를 원하는 담지량에 맞추어 투입하고, 유기용매에 황을 녹일 때와 마찬가지로, 초음파를 사용하는 것이 효과적이다. 가장 바람직하게는 반응기에 아르곤을 흘려주면서 20-40kHz, 50-100W/cm2의 초음파를 일정 시간 동안 가한다.In the process of supporting the molybdenum precursor in gamma alumina, it is effective to use ultrasonic waves as in the case of dissolving the gamma alumina and molybdenum precursor in a sulfur-organic solvent solution in accordance with a desired loading amount and dissolving sulfur in an organic solvent. Most preferably, ultrasonic waves of 20-40 kHz and 50-100 W / cm 2 are applied for a predetermined time while argon is flowed into the reactor.
마지막으로, 몰리브덴 황화물이 담지된 알루미나를 진공장치로 여과하여 세척한 후, 150-250℃에서 진공 건조하여 촉매에 남아있는 불순물을 제거한다. 이 때 세척용 유기 용매로는 헥산이나 펜탄을 사용하는 것이 바람직하나, 이에 한정하는 것은 아니다. Finally, the alumina loaded with molybdenum sulfide is filtered and washed with a vacuum apparatus, followed by vacuum drying at 150-250 ° C. to remove impurities remaining in the catalyst. At this time, it is preferable to use hexane or pentane as the organic solvent for washing, but is not limited thereto.
(A) 단계 결과, 몰리브덴을 알루미나에 함침시키는 종래 함침법으로 제조한 촉매에 비하여 몰리브덴 황화물이 고분산도로 담지된 알루미나가 얻어진다. As a result of the step (A), an alumina in which molybdenum sulfide is supported with high dispersion is obtained as compared with a catalyst prepared by a conventional impregnation method in which molybdenum is impregnated with alumina.
(B) 단계는 상기 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나에 조촉매인 코발트 및/또는 니켈 전구체를 용매에 녹여 함침하고 열처리하는 단계를 포함한다. 코발트 및/또는 니켈 전구체는 코발트 및/또는 니켈아세테이트, 코발트 및/또는 니켈할라이드, 코발트 및/또는 니켈하이드록사이드, 코발트 및/또는 니켈나이트레이트, 코발트 및/또는 니켈술페이트, 코발트 및/또는 니켈납세네이트, 코발트 및/또는 니켈아세틸아세토네이트 또는 이들의 혼합물을 사용할 수 있으며, 바람직하게는 코발트 및/또는 니켈아세틸아세토네이트이다. 코발트 및/또는 니켈 전구체를 원하는 담지량에 맞추어 용매에 용해시켜 함침하고 400℃ 미만 온도에서 열처리하며, 바람직하게는 350℃ 미만에서 열처리한다.Step (B) includes a step of impregnating and heat-treating a cobalt and / or nickel precursor which is a promoter in alumina on which molybdenum sulfide prepared in step (A) is supported in a solvent. Cobalt and / or nickel precursors may be cobalt and / or nickel acetate, cobalt and / or nickel halides, cobalt and / or nickel hydroxide, cobalt and / or nickel nitrate, cobalt and / or nickel sulfate, cobalt and / or Nickel napcenate, cobalt and / or nickelacetylacetonate or mixtures thereof may be used, preferably cobalt and / or nickelacetylacetonate. Cobalt and / or nickel precursors are dissolved in a solvent to meet the desired loading, impregnated, and heat treated at a temperature below 400 ° C., preferably at a temperature below 350 ° C.
사용 용매에는 상기 코발트 및/또는 니켈 전구체를 녹일 수 있어야 하며, H₂O, 알코올(Diol, Polyol 포함), 디메틸술폭사이드(DMSO), 디메틸포름아마이드(DMF), 디메틸아세트아마이드(DMAC), 다이그라임(Diglyme), 다이옥산, 테트라하이드로퓨란(THF) 또는 이들의 혼합물을 사용하는 것이 바람직하나, 이로 한정하는 것은 아니다.The solvent used should be capable of dissolving the cobalt and / or nickel precursors, including H 2 O, alcohols (including Diol, Polyol), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAC), and digime (Diglyme), dioxane, tetrahydrofuran (THF) or mixtures thereof are preferred, but not limited thereto.
(C) 단계는 알루미나에 담지된 코발트 및/또는 니켈 및 몰리브덴을 최종 황화물 상태로 전환하는 단계로, 코발트 및/또는 니켈-몰리브덴이 담지된 알루미나를 황화제와 용매와 함께 반응기에 넣고, 바람직하게는 200-400℃의 온도, 20-60bar의 수소압력 하에서 2-6시간 반응시킨다.Step (C) is a step of converting cobalt and / or nickel and molybdenum supported on alumina to a final sulfide state, in which alumina loaded with cobalt and / or nickel-molybdenum is added together with a sulfiding agent and a solvent, preferably The reaction is carried out for 2-6 hours at a temperature of 200-400 ℃, hydrogen pressure of 20-60bar.
사용 용매에는 도데칸, 펜타데칸, 헥사데칸 또는 이들의 혼합물을 사용하는 것이 좋으며, 이로 한정하는 것은 아니다. 황화제로 디메틸디설파이드, 디메틸설파이드, 부탄티올 또는 이들의 혼합물을 사용할 수 있으며, 이로 한정하는 것은 아니다.It is preferable to use dodecane, pentadecane, hexadecane or a mixture thereof as the solvent, but is not limited thereto. As the sulfiding agent, dimethyl disulfide, dimethyl sulfide, butane thiol or mixtures thereof may be used, but not limited thereto.
촉매 중 몰리브덴 함량은 바람직하게는, 3-50중량%, 코발트 및/또는 니켈함량을 1-20%중량이 되도록 한다. The molybdenum content in the catalyst is preferably such that 3-50% by weight, cobalt and / or nickel content is 1-20% by weight.
상기 공정을 통하여 제조된 촉매는 주촉매인 몰리브덴 황화물이 담체 위에 고분산도로 담지되어 있고, 조촉매인 코발트 및/또는 니켈이 몰리브덴 황화물 표면에 선택적으로 담지되어 있기 때문에 종래기술에 의해 제조된 촉매에 비하여 더욱 우수한 탈황성능을 나타낸다.The catalyst prepared through the above process is a catalyst prepared according to the prior art because molybdenum sulfide as a main catalyst is supported on a carrier with high dispersion and cobalt and / or nickel are selectively supported on the surface of molybdenum sulfide. It shows more excellent desulfurization performance.
본 발명에 의하면, 주촉매인 몰리브덴 황화물이 알루미나 담체 위에 고분산도로 담지되고, 조촉매인 코발트 및/또는 니켈 아세틸아세토네이트를 함침한 다음, 최적의 열처리 조건을 적용시켜 탈황 성능이 우수한 심도 탈황용 알루미나 담지 몰리브덴 황화물 촉매를 제조할 수 있다.According to the present invention, molybdenum sulfide as a main catalyst is supported on alumina carrier with high dispersion, impregnated with cobalt and / or nickel acetylacetonate as a cocatalyst, and then applied to an optimal heat treatment condition for depth desulfurization. An alumina supported molybdenum sulfide catalyst can be prepared.
본 발명의 구성은 하기 실시예에 의해 더욱 명확해질 것이며, 비교예와의 비 교에서 그 효과가 입증될 것이다.The construction of the present invention will be further clarified by the following examples, the effect of which will be demonstrated in comparison with the comparative example.
<실시예 1>≪ Example 1 >
A. 알루미나 담지 몰리브덴 황화물 촉매 제조 A. Preparation of Alumina Supported Molybdenum Sulfide Catalyst
황 0.13g, 헥사데칸 65cc, 1,3,5-트리메틸벤젠 5cc를 용량 100cc 반응기에 넣고, 반응기의 온도를 60℃로 유지하면서 20 kHz, 80W/cm2의 초음파를 20분 동안 가하여 황을 용매에 완전히 용해시켰다. 0.13 g of sulfur, 65 cc of hexadecane, 1 cc of 1,3,5-trimethylbenzene were placed in a 100 cc reactor, and the sulfur was dissolved by applying 20 kHz, 80 W / cm 2 ultrasonic wave for 20 minutes while maintaining the reactor temperature at 60 ° C. Completely dissolved.
이어서, 몰리브덴 전구체로 몰리브덴 헥사카르보닐 0.53g과 감마 알루미나 1.0g을 반응기에 넣고, 60℃에서 아르곤을 25cc/min의 유량으로 반응기 내로 유입시키면서 20kHz, 80W/cm2의 초음파를 1시간 30분 동안 가하여 알루미나에 몰리브덴 황화물을 담지시킨 후, 과량의 헥산으로 세척하여 유기용매를 제거하고, 200℃에서 2시간 동안 진공 건조하여 잔류 불순물을 제거하였다.Subsequently, 0.53 g of molybdenum hexacarbonyl and 1.0 g of gamma alumina were added to the reactor as a molybdenum precursor, and ultrasonic waves at 20 kHz and 80 W / cm 2 were introduced for 1 hour and 30 minutes while argon was introduced into the reactor at a flow rate of 25 cc / min at 60 ° C. After adding molybdenum sulfide to the alumina, the resultant was washed with excess hexane to remove the organic solvent, followed by vacuum drying at 200 ° C. for 2 hours to remove residual impurities.
B. 니켈 담지B. Nickel Support
니켈 전구체로 니켈아세틸아세토네이트 0.0922g을 DMSO 1.2g에 녹여 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나 0.4g에 함침시킨 후 230℃ 공기 분위기에서 열처리하여 DMSO를 제거한다. 건조 된 촉매는 (C) 단계에서와 같은 방법으로 황화한다. 제조된 니켈-몰리브덴 황화물 촉매의 니켈 함량은 5중량%이고, 몰리브덴 함량은 10중량%이었다. 0.0922 g of nickel acetylacetonate as a nickel precursor was dissolved in 1.2 g of DMSO, and then impregnated in 0.4 g of alumina loaded with molybdenum sulfide prepared in step (A), followed by heat treatment in an air atmosphere at 230 ° C. to remove DMSO. The dried catalyst is sulfided in the same way as in step (C). The nickel content of the prepared nickel-molybdenum sulfide catalyst was 5% by weight, and the molybdenum content was 10% by weight.
C. 촉매의 황화C. Sulfurization of the Catalyst
상기 (B) 단계에서 제조된 몰리브덴 황화물과 니켈이 담지된 알루미나 0.3g, 펜타데칸 (용매) 10cc 및 황화제로 디메틸디설파이드 2cc를 반응기에 넣고, 40bar의 수소압력 하에서 300℃로 유지하면서 1,000rpm으로 교반하면서 4시간 동안 반응시켜 촉매를 황화시킨 후, 헥산으로 세척하고, 상온에서 진공 건조시켰다.0.3 g of molybdenum sulfide and nickel prepared in step (B), 10 cc of pentadecane (solvent), and 2 cc of dimethyl disulfide were added to the reactor with a sulfiding agent, and stirred at 1,000 rpm while maintaining the temperature at 300 ° C. under a hydrogen pressure of 40 bar. After reacting for 4 hours while sulfiding the catalyst, washed with hexane, and dried under vacuum at room temperature.
<비교예 1>Comparative Example 1
실시예 1의 (B) 단계에서 제조한 촉매를 공기 분위기에서 400℃로 열처리하는 것을 제외하고는 실시예 1과 동일한 방법으로 촉매를 제조하였다. 제조된 니켈-몰리브덴 황화물 촉매의 니켈 함량은 5중량%이고, 몰리브덴 함량은 10중량%이었다.A catalyst was prepared in the same manner as in Example 1, except that the catalyst prepared in Step (B) of Example 1 was heat-treated at 400 ° C. in an air atmosphere. The nickel content of the prepared nickel-molybdenum sulfide catalyst was 5% by weight, and the molybdenum content was 10% by weight.
<비교예 2>Comparative Example 2
니켈 전구체로 니켈나이트레이트 0.1304g을 H₂O 1.2g에 녹여 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나 0.5g에 함침시키는 것을 제외하고는 실시예 1과 동일한 방법으로 촉매를 제조하였다. 제조된 니켈-몰리브덴 황화물 촉매의 니켈 함량은 5중량%이고, 몰리브덴 함량은 10중량%이었다.A catalyst was prepared in the same manner as in Example 1 except that 0.1304 g of nickel nitrate was dissolved in 1.2 g of H 2 O as a nickel precursor, and then impregnated with 0.5 g of alumina loaded with molybdenum sulfide prepared in step (A). The nickel content of the prepared nickel-molybdenum sulfide catalyst was 5% by weight, and the molybdenum content was 10% by weight.
<비교예 3>Comparative Example 3
니켈 전구체로 니켈나이트레이트 0.1304g을 H₂O 1.2g에 녹여 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나 0.5g에 함침시키고, 공기 분위기에서 400℃로 열처리하는 것을 제외하고는 실시예 1과 동일한 방법으로 촉매를 제조하였다. 제조된 니켈-몰리브덴 황화물 촉매의 니켈 함량은 5중량%이고, 몰리브덴 함량은 10중량%이었다.0.1304 g of nickel nitrate was dissolved in 1.2 g of H2O as a nickel precursor, and impregnated in 0.5 g of alumina loaded with molybdenum sulfide prepared in step (A), and then heat-treated at 400 ° C. in an air atmosphere. The catalyst was prepared by the method. The nickel content of the prepared nickel-molybdenum sulfide catalyst was 5% by weight, and the molybdenum content was 10% by weight.
<실험예 1>Experimental Example 1
실시예 1과 비교예 1, 2, 3에서 제조한 촉매를 실시예 1의 (C) 촉매 황화 공정을 수행한 다음, 디벤조티오펜 탈황반응을 아래의 방법으로 실시하였고 그 결과는 표1에 기재하였다.The catalysts prepared in Example 1 and Comparative Examples 1, 2, and 3 were subjected to the catalytic sulfidation process of Example 1, and then the dibenzothiophene desulfurization reaction was carried out by the following method. Described.
1. 반응 실험1. Reaction experiment
디벤조티오펜 0.03g을 펜타데칸 30cc에 용해시켜 촉매 0.09g과 함께 고압반응기에 넣고, 320℃에서 40bar의 수소를 유입시켜 30분간 탈황반응을 수행하였다. 0.03 g of dibenzothiophene was dissolved in 30 cc of pentadecane and placed in a high pressure reactor together with 0.09 g of a catalyst, and desulfurization was performed for 30 minutes by introducing 40 bar of hydrogen at 320 ° C.
[표1] Table 1
조촉매인 니켈 전구체로 니켈아세틸아세토네이트를 함침한 촉매의 활성이 니켈나이트레이트를 함침한 촉매보다 우수하였다. 또한, 니켈을 담지한 후 400℃에서 소성한 촉매의 활성이 열세하였다.The activity of the catalyst impregnated with nickel acetylacetonate as the cocatalyst nickel precursor was superior to the catalyst impregnated with nickel nitrate. In addition, the activity of the catalyst calcined at 400 ° C. after supporting nickel was inferior.
즉, 상기 촉매는 조촉매 전구체뿐만 아니라, 함침 후 열처리 조건도 촉매 활성에 영향을 미치는 중요인자로 작용함을 알 수 있다.That is, it can be seen that the catalyst acts as an important factor that affects the catalyst activity, as well as the cocatalyst precursor and the heat treatment conditions after impregnation.
<실시예 2><Example 2>
코발트 전구체로 코발트아세틸아세토네이트 0.056g을 DMSO 0.35g에 녹여 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나 0.35g에 함침시키는 것을 제외하고는 실시예 1과 동일한 방법으로 촉매를 제조하고, 실시예 1의 (C)방법으로 촉매를 황화하였다. 제조된 코발트-몰리브덴 황화물 촉매의 코발트 함량은 3중량%이고, 몰리브덴 함량은 10중량%이었다.A catalyst was prepared in the same manner as in Example 1, except that 0.056 g of cobalt acetylacetonate was dissolved in 0.35 g of DMSO as a cobalt precursor, and then impregnated in 0.35 g of alumina loaded with molybdenum sulfide prepared in step (A). The catalyst was sulfided by the method (C) in Example 1. The cobalt content of the prepared cobalt-molybdenum sulfide catalyst was 3% by weight, and the molybdenum content was 10% by weight.
<비교예 4><Comparative Example 4>
코발트 전구체로 코발트나이트레이트 0.054g을 H₂O 0.35g에 녹여 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나 0.35g에 함침시키는 것을 제외하고는 실시예 1과 동일한 방법으로 촉매를 제조하고, 실시예 1의 (C)방법으로 촉매를 황화하였다. 제조된 코발트-몰리브덴 황화물 촉매의 코발트 함량은 3중량%이고, 몰리브덴 함량은 10중량%이었다. A catalyst was prepared in the same manner as in Example 1, except that 0.054 g of cobalt nitrate was dissolved in 0.35 g of H 2 O as a cobalt precursor, and then impregnated with 0.35 g of alumina loaded with molybdenum sulfide prepared in step (A). The catalyst was sulfided by the method (1). The cobalt content of the prepared cobalt-molybdenum sulfide catalyst was 3% by weight, and the molybdenum content was 10% by weight.
<비교예 5>Comparative Example 5
알루미나 6g에 몰리브덴 전구체로 암모늄헵타몰리브데이트 2.15g을 H2O 1.5g에 용해시키고, 알루미나 6g에 함침 시킨 다음, 150℃에서 2시간 건조하고, 500℃에서 2시간 소성하여 몰리브덴이 담지된 알루미나를 제조하였다. 또한, 코발트를 담지하기 위하여 코발트나이트레이트 0.75g을 H2O 2.1g에 용해시키고 몰리브덴이 담지된 알루미나에 함침시킨 다음 150℃에서 2시간 건조하고, 500℃에서 2시간 소성하여 코발트-몰리브덴 산화물이 담지된 알루미나 촉매를 제조하였다.In 6 g of alumina, 2.15 g of ammonium heptamolybdate as a molybdenum precursor was dissolved in 1.5 g of H 2 O, impregnated in 6 g of alumina, dried at 150 ° C. for 2 hours, and calcined at 500 ° C. for 2 hours to carry molybdenum-supported alumina. Was prepared. In addition, in order to support cobalt, 0.75 g of cobalt nitrate was dissolved in 2.1 g of H 2 O, impregnated in alumina loaded with molybdenum, dried at 150 ° C. for 2 hours, and calcined at 500 ° C. for 2 hours to obtain cobalt-molybdenum oxide. A supported alumina catalyst was prepared.
상기 방법으로 제조된 코발트-몰리브덴 산화물이 담지된 알루미나 0.3g, 펜타데칸 (용매) 10cc 및 황화제로 디메틸디설파이드 2cc를 반응기에 넣고, 40bar의 수소압력 하에서 350℃로 유지하면서 1,000rpm으로 교반하면서 4시간 동안 반응시켜 촉매를 황화시킨 후, 헥산으로 세척하고, 상온에서 진공 건조시켰다.0.3 g of alumina loaded with cobalt-molybdenum oxide prepared by the above method, 10 cc of pentadecane (solvent), and 2 cc of dimethyl disulfide were added to a reactor with a sulfiding agent, and stirred at 1,000 rpm while maintaining the temperature at 350 ° C. under a hydrogen pressure of 40 bar for 4 hours. The reaction was followed by sulfidation of the catalyst, washing with hexane, and vacuum drying at room temperature.
제조된 코발트-몰리브덴 황화물 촉매의 코발트 함량은 3중량%이고, 몰리브덴 함량은 10중량%이었다.The cobalt content of the prepared cobalt-molybdenum sulfide catalyst was 3% by weight, and the molybdenum content was 10% by weight.
<비교예 6>Comparative Example 6
코발트트리카르보닐니트로실을 화학 증착하는 종래의 기술과 비교하기 위하여 촉매를 제조하였다. 코발트 전구체로 코발트트리카르보닐니트로실 3cc와 (A) 단계에서 제조된 몰리브덴 황화물이 담지된 알루미나 0.3g을 기화반응기에 넣고, 상온에서 질소를 24cc/min의 유량으로 5분간 유입시켜 몰리브덴 황화물이 담지된 알루미나에 전구체를 증착시켰다.Catalysts were prepared for comparison with conventional techniques for chemical vapor deposition of cobalttricarbonylnitrosyl. 3 cc of cobalt tricarbonylnitrosyl as a cobalt precursor and 0.3 g of alumina loaded with molybdenum sulfide prepared in step (A) were put into a vaporization reactor, and nitrogen was introduced at a flow rate of 24 cc / min for 5 minutes at room temperature to carry molybdenum sulfide. The precursor was deposited on the alumina.
이어서, 질소를 30cc/min의 유량으로 30분간 통과시켜 물리적으로 흡착된 코발트 전구체를 제거하고, 질소를 20cc/min의 유량으로 1시간 동안 흘리며 200℃에서 열처리를 하여 코발트 전구체에 존재하는 카르보닐기 및 니트로실기등의 리간드를 제거하였다. 이러한 화학 증착법을 5회 반복하여, 코발트 함량은 3.5중량%이고, 몰리브덴 함량은 10중량%인 코발트-몰리브덴 황화물 촉매를 제조하였으며, 실시예 1의 (C)방법으로 촉매를 황화하였다.Subsequently, nitrogen was passed through a flow rate of 30 cc / min for 30 minutes to remove the physically adsorbed cobalt precursor, and nitrogen was flowed for 1 hour at a flow rate of 20 cc / min, followed by heat treatment at 200 ° C. to form carbonyl groups and nitro groups present in the cobalt precursor. Ligands, such as a practical group, were removed. This chemical vapor deposition was repeated five times to prepare a cobalt-molybdenum sulfide catalyst having a cobalt content of 3.5% by weight and a molybdenum content of 10% by weight, and the catalyst was sulfided by the method (C) of Example 1.
<실험예 2> Experimental Example 2
실시예 2와 비교예 4, 5, 6에서 제조한 촉매의 디벤조티오펜 탈황반응을 실시예 1의 방법으로 실시하였고, 40분간 반응 후 그 결과를 표 2에 기재하였다.The dibenzothiophene desulfurization reaction of the catalysts prepared in Example 2 and Comparative Examples 4, 5 and 6 was carried out by the method of Example 1, and the results are shown in Table 2 after the reaction for 40 minutes.
<표 2>TABLE 2
본 발명에 따라 제조된 실시예 2의 코발트아세틸아세토네이트 촉매의 탈황 활성이 가장 우수하였다.The desulfurization activity of the cobaltacetylacetonate catalyst of Example 2 prepared according to the present invention was the best.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090119870A KR101631321B1 (en) | 2009-12-04 | 2009-12-04 | Preparation of cobalt and/or nickel-molybdenum sulfide sulfide catalyst supported on alumina for deep hydrodesulfurization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090119870A KR101631321B1 (en) | 2009-12-04 | 2009-12-04 | Preparation of cobalt and/or nickel-molybdenum sulfide sulfide catalyst supported on alumina for deep hydrodesulfurization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20110062968A true KR20110062968A (en) | 2011-06-10 |
| KR101631321B1 KR101631321B1 (en) | 2016-06-17 |
Family
ID=44397056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020090119870A KR101631321B1 (en) | 2009-12-04 | 2009-12-04 | Preparation of cobalt and/or nickel-molybdenum sulfide sulfide catalyst supported on alumina for deep hydrodesulfurization |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101631321B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002374A (en) * | 2017-12-14 | 2018-05-08 | 合肥工业大学 | A kind of ultra-thin two-dimension stratified material nanometer sheet and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106422712A (en) * | 2016-12-07 | 2017-02-22 | 陈佐会 | High-pressure spray desulfurization, denitration and dust removal method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030047416A (en) * | 2001-12-10 | 2003-06-18 | 에스케이 주식회사 | Method for preparing molybdenum sulfide-alumina catalyst for desulfurization |
| KR20060020151A (en) * | 2004-08-31 | 2006-03-06 | 재단법인서울대학교산학협력재단 | Preparation of cobalt-molybdenum sulfide catalyst supported on alumina for deep hydrodesulfurization |
-
2009
- 2009-12-04 KR KR1020090119870A patent/KR101631321B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030047416A (en) * | 2001-12-10 | 2003-06-18 | 에스케이 주식회사 | Method for preparing molybdenum sulfide-alumina catalyst for desulfurization |
| KR20060020151A (en) * | 2004-08-31 | 2006-03-06 | 재단법인서울대학교산학협력재단 | Preparation of cobalt-molybdenum sulfide catalyst supported on alumina for deep hydrodesulfurization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002374A (en) * | 2017-12-14 | 2018-05-08 | 合肥工业大学 | A kind of ultra-thin two-dimension stratified material nanometer sheet and preparation method thereof |
| CN108002374B (en) * | 2017-12-14 | 2021-03-19 | 合肥工业大学 | Ultrathin two-dimensional layered material nanosheet and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101631321B1 (en) | 2016-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5264029B2 (en) | Production of hydrotreating catalyst | |
| JP5015818B2 (en) | Gas oil hydrotreating catalyst, method for producing the same, and gas oil hydrotreating method | |
| CN109794257B (en) | Sulfur-tolerant shift catalyst and preparation method thereof | |
| CN109289876B (en) | Deep desulfurization catalyst and preparation method and application thereof | |
| CN107469836B (en) | Sulfur tail gas hydrogenation catalyst and preparation method thereof | |
| CN111468142A (en) | Co-Mo-S catalyst and preparation method thereof | |
| CN110354871B (en) | Hydrogenation catalyst, preparation method and application thereof, and hydrofining method | |
| JP4519719B2 (en) | Method for producing hydrotreating catalyst for hydrocarbon oil, and hydrotreating method for hydrocarbon oil | |
| KR20110062968A (en) | Preparation of cobalt and/or nickel-molybdenum sulfide sulfide catalyst supported on alumina for deep hydrodesulfurization | |
| CN108722441B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN112827501A (en) | Controllable synthesis of alpha-MoC supported indium and modified catalyst thereof and application of alpha-MoC supported indium in reaction for preparing methanol by carbon dioxide hydrogenation | |
| CN112604709B (en) | Hydrogenation catalyst for sulfur-containing waste gas treatment and application thereof | |
| CN106607102B (en) | Alumina carrier, preparation method and application thereof | |
| JP2013027838A (en) | Method of regenerating hydrogenation catalyst | |
| KR100619333B1 (en) | Method for preparing molybdenum sulfide-alumina catalyst for desulfurization | |
| KR100586163B1 (en) | Preparation of cobalt-molybdenum sulfide catalyst supported on alumina for deep hydrodesulfurization | |
| CN113893867A (en) | Preparation method of hydrodesulfurization catalyst with mesoporous carbon material as carrier | |
| CN110508294B (en) | Preparation method of hydrogenation catalyst, hydrogenation catalyst prepared by method and application of hydrogenation catalyst | |
| CN112705246A (en) | Desulfurization and dearomatization catalyst and preparation method thereof | |
| CN111378489B (en) | Startup method of hydrogenation device | |
| CN108726573B (en) | Tetrathiomolybdate solution, preparation method and application thereof | |
| CN115999585B (en) | Supported sulfidation hydrogenation catalyst with atomic dispersion Mo as auxiliary agent, and preparation method and application thereof | |
| CN115869985B (en) | Atomic dispersion Mo modified supported sulfidation hydrogenation catalyst and preparation method and application thereof | |
| JP2020534140A (en) | Method for manufacturing metal-containing catalyst | |
| CN115814826A (en) | Hydrodesulfurization and denitrification catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20190325 Year of fee payment: 4 |