JPH0386247A - Method for activating sulfide precursor type hydrogenation catalyst - Google Patents
Method for activating sulfide precursor type hydrogenation catalystInfo
- Publication number
- JPH0386247A JPH0386247A JP22043489A JP22043489A JPH0386247A JP H0386247 A JPH0386247 A JP H0386247A JP 22043489 A JP22043489 A JP 22043489A JP 22043489 A JP22043489 A JP 22043489A JP H0386247 A JPH0386247 A JP H0386247A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- temperature
- temp
- sulfide
- sulfurization
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 5
- 230000003213 activating effect Effects 0.000 title claims description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 230000000977 initiatory effect Effects 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000005486 sulfidation Methods 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 10
- 230000023556 desulfurization Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005987 sulfurization reaction Methods 0.000 abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000003921 oil Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 150000002898 organic sulfur compounds Chemical class 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は炭化水素油の水素化脱硫反応に用いられる、有
機イオウ化合物を硫化物として含有せしめた硫化物前駆
体型水素化処理触媒の活性化方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the activation of a sulfide precursor-type hydrotreating catalyst containing an organic sulfur compound as a sulfide, which is used in the hydrodesulfurization reaction of hydrocarbon oil. It is about the method.
［従来の技術］
一般に炭化水素油の水素化脱硫反応に用いられる触媒に
は、γ−アルミナ、シリカ−アルミナ等の無機酸化物担
体に、周期率表第６族金属及び第８族金属から選ばれる
少なくとも一種の金属を水素化活性成分として担持せし
めたものが用いられている。最も一般的には、第６族金
属としてモリブデンが用いられ、第８族金属としてニッ
ケルやコバルトが用いられる。これらの金属活性成分は
調製後には通常酸化物態で担持されており、そのままで
は活性がないため、水素化処理反応に供するためには酸
化物状態から硫化物態に変換する予備硫化、いわゆる活
性化が必要である。この活性化方法として、硫化水素や
メルカプタン類のような有機イオウ化合物を軽油に混合
し、固定触媒層に流通する方法が一般的に採用されてい
る。[Prior Art] Catalysts used in the hydrodesulfurization reaction of hydrocarbon oils generally include an inorganic oxide support such as γ-alumina or silica-alumina, and a metal selected from Group 6 metals and Group 8 metals of the periodic table. At least one metal supported as a hydrogenation active component is used. Most commonly, molybdenum is used as the Group 6 metal, and nickel or cobalt is used as the Group 8 metal. These metal active components are usually supported in an oxide state after preparation, and are not active as they are. Therefore, in order to use them for the hydrogenation reaction, they must be pre-sulfided to convert from an oxide state to a sulfide state, so-called activation. It is necessary to As a method for this activation, a method is generally adopted in which organic sulfur compounds such as hydrogen sulfide and mercaptans are mixed with light oil and the mixture is passed through a fixed catalyst bed.
［発明が解決しようとする課題］
ところが、これらの方法では二硫化が完全に進行するま
での必要時間は数日にわたり、硫化終了を判断すること
が困難であるという欠点がある。[Problems to be Solved by the Invention] However, these methods have the disadvantage that it takes several days for disulfidation to proceed completely, making it difficult to judge when sulfurization has finished.
しかも１．硫化操作は一次的なものであるため自動化さ
れていないことが多く、通常と異なる繁雑な操作が要求
されている。Moreover, 1. Since the sulfiding operation is temporary, it is often not automated and requires a different and more complicated operation than usual.
近時、これらの硫化方法よりも一段と効率のよい硫化方
法が特開昭６１−１１１１４４号公報に開示されている
。即ち、予め酸化物型の触媒に以下の構造式で示される
有機イオウ化合物を添加し、硫化物前駆体としておく方
法である。Recently, a sulfurization method that is even more efficient than these sulfurization methods has been disclosed in Japanese Patent Application Laid-Open No. 111144/1983. That is, this is a method in which an organic sulfur compound represented by the following structural formula is added to an oxide type catalyst in advance to form a sulfide precursor.
（ジターシャリ−ノニル・ポリスルフィド）ここでｎは
４〜２０の整数である。(Ditertiary-nonyl polysulfide) where n is an integer from 4 to 20.
該有機イオウ化合物は、触媒中の活性金属がほぼ硫化物
となる必要量が添加されており、脱硫反応温度附近まで
加熱された水素ガスや反応原料油を触媒層に通し昇温す
ることのみによって活性成分を硫化することができ、短
時間での脱硫操業の開始を可能とするものである。The organic sulfur compound is added in the necessary amount so that the active metal in the catalyst becomes almost sulfide, and it is only by raising the temperature by passing hydrogen gas or reaction raw material heated to around the desulfurization reaction temperature through the catalyst layer. The active ingredient can be sulfurized and desulfurization operations can be started in a short time.
この活性化方法を具体的に示すと以下のようになる。A concrete example of this activation method is as follows.
第一に反応装置の保全のために！！−を圧充し、機密試
験を行なう。この試験は反応装置の水素脆化を避けるた
め、通常１５０〜２５０°Ｃで行なう。First of all, for the preservation of the reactor! ! −, and perform a secret test. This test is normally conducted at 150-250°C to avoid hydrogen embrittlement of the reactor.
次いで、反応原料油の流通を開始する。また、条件によ
っては、原料油を循環させる場合もある。Next, distribution of the reaction raw material oil is started. Also, depending on the conditions, the raw material oil may be circulated.
このようにして行なう触媒層の昇温速度は常用の平均値
として０．３℃／ｍｉｎ前後である。従って、水素化脱
硫反応温度を３３０°Ｃと仮定すると昇温に要する時間
は４．４〜ｌＯ時間となる。The heating rate of the catalyst layer carried out in this way is about 0.3° C./min as a common average value. Therefore, assuming that the hydrodesulfurization reaction temperature is 330°C, the time required to raise the temperature is 4.4 to 10 hours.
ところが、硫化物前駆体型水素化処理触媒を上記のよう
に実際の製油所の設備や運転条件に従って活性化し、水
素化脱硫反応を行なうと、触媒初期の活性が充分発揮さ
れないという問題点が生じた。触媒の初期活性が低いこ
とは、結果的に触媒能力が低いことになり、それゆえに
硫化物前駆体型水素化処理触媒を用いる上での適切な活
性化の方法の開発が望まれている。However, when a sulfide precursor-type hydrotreating catalyst is activated according to the actual refinery equipment and operating conditions as described above and a hydrodesulfurization reaction is carried out, a problem arises in that the initial activity of the catalyst is not sufficiently exerted. . A low initial activity of the catalyst results in a low catalytic ability, and therefore, it is desired to develop an appropriate activation method when using a sulfide precursor type hydrotreating catalyst.
本発明の目的は、硫化物前駆体型水素化処理触媒を活性
化する際の適切な方法を提供することにある。An object of the present invention is to provide a suitable method for activating a sulfide precursor type hydrotreating catalyst.
［課題を解決するための手段］
本発明者らは、製油所での運転で施される種々の条件の
脱硫活性に対する影響を調べた結果、活性化時の昇温速
度が大きく影響することを見出し、更に検討を重ねた結
果、本発明に至った。[Means for Solving the Problem] As a result of investigating the effects of various conditions applied during refinery operation on desulfurization activity, the present inventors found that the rate of temperature increase during activation has a large effect. As a result of this finding and further studies, we have arrived at the present invention.
即ち、上記課題を解決するための本発明の方法は周期率
表第６族金属と第８族金属から選ばれる少なくとも一種
の金属を水素化活性成分として含むアルミナ担持触媒に
硫化剤を含有せしめて調製された硫化物前駆体型水素化
脱硫触媒を活性化する方法において、触媒層の温度が少
なくとも１５０°Ｃより前記活性成分の硫化反応開始温
度までの昇温速度を０．５°Ｃ／ ｗｉｎ以上とするも
のである。That is, the method of the present invention for solving the above problems involves incorporating a sulfiding agent into an alumina-supported catalyst containing at least one metal selected from Group 6 metals and Group 8 metals of the periodic table as a hydrogenation active component. In the method of activating the prepared sulfide precursor-type hydrodesulfurization catalyst, the temperature of the catalyst layer is increased from at least 150°C to the sulfidation reaction initiation temperature of the active ingredient at a rate of 0.5°C/win or more. That is.
［作用］
本発明を説明すに際し、まず、硫化剤の分解反応に伴い
進行する活性金属の硫化の過程を説明する。[Function] In explaining the present invention, first, the process of sulfurization of the active metal, which progresses along with the decomposition reaction of the sulfurizing agent, will be explained.
有機イオウ化合物である硫化剤を以下のように表す。The sulfurizing agent, which is an organic sulfur compound, is expressed as follows.
メルカプタン類： Ｒ−Ｓ −Ｉｔ スルフィド類 ：Ｒ−Ｓ−Ｒ’ ここでＲ，Ｒ’はアルキル基である。Mercaptans: R-S-It Sulfides: R-S-R' Here, R and R' are alkyl groups.
硫化剤の分解と硫化反応は以下のようになる。The decomposition of the sulfurizing agent and the sulfurization reaction are as follows.
２Ｒ−ＳＨ＋ Ｍｏ（ＩＶ、ＶＩ） ＝ＭＯＳ！＋炭化
水素 ■２Ｒ−Ｓ−Ｒ’ ＋ Ｍｏ（ＩＶ、Ｖｌ）
＝ ＭｏＳ、十炭化水素 ■硫化反応による硫化モリブ
デンの生成反応はや＜３００°Ｃで始り、温度が高くな
ればなるほど促進されることは周知のとうりである。一
方で硫化剤として使用される有機イオウ化合物は分解温
度が約１５０〜２００°Ｃ程度のものがほとんどである
。従って昇温中１５０〜３００°Ｃの範囲では硫化剤の
分解により発生したイオウ分は、活性金属を硫化するこ
となく、硫化水素やメルカプタンとなって脱離してしま
う。2R-SH+ Mo(IV, VI) = MOS! + Hydrocarbon ■2R-S-R' + Mo (IV, Vl)
= MoS, 10 hydrocarbons ■ It is well known that the production reaction of molybdenum sulfide by sulfurization reaction starts at <300°C and accelerates as the temperature increases. On the other hand, most organic sulfur compounds used as sulfurizing agents have a decomposition temperature of about 150 to 200°C. Therefore, during temperature rise in the range of 150 to 300°C, the sulfur component generated by decomposition of the sulfurizing agent does not sulfurize the active metal, but is desorbed as hydrogen sulfide or mercaptan.
本発明において触媒層の温度が少なくとも１５０°Ｃよ
り水素化処理反応の開始温度までの昇温速度を０．５°
Ｃ／ ｗｉｎ以上とするのは、１５０’Ｃ以下では、使
用し得る硫化剤のほとんどが安定であり、分解しないか
らであり、０．５ ”Ｃ／ ｓｉｎ未満の昇温速度では
硫化の効率がなんら改良されないからである。無論、昇
温速度は大きければ大きいほど好ましいが、現実には用
いる各装置の能力があり、これが上限となる。また、活
性成分の硫化反応開始温度とは、活性成分の違いはある
が、おおよそ３００°Ｃである。In the present invention, the temperature of the catalyst layer is increased by at least 0.5° from 150°C to the starting temperature of the hydrotreating reaction.
The reason for setting it above C/win is that below 150'C, most of the sulfurizing agents that can be used are stable and do not decompose, and at a heating rate of less than 0.5''C/sin, the sulfiding efficiency decreases. This is because no improvement will be made.Of course, the higher the temperature increase rate, the better, but in reality, each device used has its own capacity, and this is the upper limit.In addition, the sulfurization reaction initiation temperature of the active ingredient is Although there are differences, it is approximately 300°C.
［実施例コ
三酸化モリブデン２９．０ ｇ、炭酸コバルト１２．５
ｇ、８５％正リン酸 １６．５ ｇ、純度８５％のメル
カプト酢酸２４．．１ｇおよび１４０ ｇの擬ベーマイ
トを水を用いて混練し、直径２■の円筒型に成型した後
、空気中にて、１００°Ｃで１８時間乾燥し、平均軸長
が３１１１ｍになるように切断して硫化物前駆体型水素
化処理触媒を得た。[Example 29.0 g of molybdenum trioxide, 12.5 g of cobalt carbonate]
g, 85% orthophosphoric acid 16.5 g, 85% purity mercaptoacetic acid 24. ．． 1g and 140g of pseudo-boehmite were kneaded with water, molded into a cylindrical shape with a diameter of 2mm, dried in air at 100°C for 18 hours, and cut into pieces with an average axial length of 3111m. A sulfide precursor type hydrotreating catalyst was obtained.
次いで、内径１．５ｃｍである反応管に、充填容積が１
５ ｃｃとなるように前記触媒を充填した。Then, a reaction tube with an inner diameter of 1.5 cm was filled with a filling volume of 1
The catalyst was filled to a volume of 5 cc.
この反応管を流通系反応装置に連結した後、水素圧力を
３０ ｋｇ／ｃ＋ｓ”−Ｇ、水素流通線速度１５０ ｃ
ｍ／ｈｒとして流通し、同時にクラエート常圧軽油を時
空間遠度４ ｈｒ−で流通した。触媒層の温度が３００
°Ｃになるまで０．８３℃／ｍｉｎの昇温速度で昇温し
、その後、以下の条件で脱硫水素化反応を開始した。After connecting this reaction tube to a flow system reactor, the hydrogen pressure was set to 30 kg/c+s''-G, and the hydrogen flow linear velocity was set to 150 c.
m/hr, and at the same time, claate atmospheric gas oil was distributed at a time and space distance of 4 hr. The temperature of the catalyst layer is 300
The temperature was raised at a temperature increase rate of 0.83°C/min until the temperature reached 0.°C, and then the hydrogen desulfurization reaction was started under the following conditions.
通油時空間速度（ＬＩＩＳＩ／） ２ Ｈｒ−’水素
圧力 ３０ Ｋｇ／ｃｍ”−Ｇ水素流通方
向線速度 １５０ ａｍ／ｈｒ反応時間
４８時間
反応原料油 クラエート常圧軽油（イオウ含有率
１．５５％）
水素加脱硫反応の結果、平均脱硫活性率は反応次数を１
．７５次として求められた速度定数として８．５を示し
た。この値は、通常製油所でとられる平均的な昇温速度
０，２℃／ｍｉｎで昇温した場合に較べて高く、比較例
より約３０ ％も高いものであった。Oil passing hourly space velocity (LIISI/) 2 Hr-'Hydrogen pressure 30 Kg/cm"-G hydrogen flow direction linear velocity 150 am/hrReaction time
48-hour reaction feedstock oil Kraate atmospheric gas oil (sulfur content 1.55%) As a result of the hydrovulcanization reaction, the average desulfurization activity was 1 reaction order
．． The rate constant determined as the 75th order was 8.5. This value was higher than when the temperature was raised at the average temperature increase rate of 0.2°C/min normally used in oil refineries, and was about 30% higher than that of the comparative example.
［比較例コ
実施例１と同し触媒を、同様の反応管に充填し、流通系
反応装置に連結した後、水素圧力を３０ｋｇ／ｃｒａ”
−Ｇｓ水素流通線速度１５０ ｃｍ／ｈｒとなるように
水素を流入させつつ、クラエート常圧軽油を時空間速度
（ＬＨＳＶ）が４ ｈｒ−’ となるように流入させ、
通常の製油所の平均昇温速度である０、２０℃／ｍｉｎ
の昇温速度で３３０°Ｃまで昇温し、引続き以下の条件
で脱硫水素化反応を行なった。[Comparative Example: The same catalyst as in Example 1 was filled into a similar reaction tube, and after connecting it to a flow system reactor, the hydrogen pressure was set at 30 kg/cra.
-Gs While hydrogen is flowing at a linear velocity of 150 cm/hr, claate atmospheric gas oil is flowing at a space-time velocity (LHSV) of 4 hr-',
0, 20℃/min, which is the average temperature increase rate in a normal refinery
The temperature was raised to 330° C. at a temperature increase rate of 330° C., and the hydrogen desulfurization reaction was subsequently carried out under the following conditions.
通油時空間速度（ＬＩＩＳＶ） ２１１ｒ”水素圧力
３０ Ｋｇ／ｃｍ’−Ｇ水素流通方向線
速度 １５０ ａｍ／ｈｒ反応時間 ４８
時間
反応原料油 クラエート常圧軽油（イオウ含有率
１．５５％）
水素加脱硫反応の結果、平均脱硫活性率は反応次数を１
．７５次として求められた速度定数として５．９を示し
た。この値は、実施例より ３０％も低いものであった
。これは、長時間にわたる昇温の影響を受けたものと思
われる。Oil passing hourly space velocity (LIISV) 211r"Hydrogen pressure 30 Kg/cm'-G hydrogen flow direction linear velocity 150 am/hrReaction time 48
Time-reactive feedstock oil Claate atmospheric gas oil (sulfur content 1.55%) As a result of the hydrodesulfurization reaction, the average desulfurization activity is 1 reaction order
．． The rate constant determined as the 75th order was 5.9. This value was 30% lower than that of the example. This seems to be due to the effect of prolonged temperature rise.
［発明の効果コ
本発明の方法によれば、触媒温度を急速に上昇させるた
めるに硫化に使用し得るイオウ分の損失を最小限に押え
ることができるため触媒の初期活性を高めることができ
、その結果、高い脱硫活性を引出すことができる。[Effects of the Invention] According to the method of the present invention, the loss of sulfur content that can be used for sulfidation can be minimized by rapidly increasing the catalyst temperature, so that the initial activity of the catalyst can be increased. As a result, high desulfurization activity can be achieved.
Claims (1)
も一種の金属を水素化活性成分として含むアルミナ担持
触媒に硫化剤を含有せしめて調製された硫化物前駆体型
水素化脱硫触媒を活性化する方法において、触媒層の温
度が少なくとも１５０℃より前記活性成分の硫化反応開
始温度までの昇温速度を０．５℃／ｍｉｎ以上とするこ
とを特徴とする硫化物前駆体型水素化処理触媒の活性化
方法。Activating a sulfide precursor-type hydrodesulfurization catalyst prepared by incorporating a sulfiding agent into an alumina-supported catalyst containing at least one metal selected from Group 6 metals and Group 8 metals of the periodic table as a hydrogenation active component. In the method, the temperature of the sulfide precursor type hydrotreating catalyst is characterized in that the temperature of the catalyst layer is increased from at least 150°C to the sulfidation reaction initiation temperature of the active component at a rate of 0.5°C/min or more. Activation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1220434A JP2863559B2 (en) | 1989-08-29 | 1989-08-29 | Activation method of sulfide precursor type hydrotreating catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1220434A JP2863559B2 (en) | 1989-08-29 | 1989-08-29 | Activation method of sulfide precursor type hydrotreating catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0386247A true JPH0386247A (en) | 1991-04-11 |
| JP2863559B2 JP2863559B2 (en) | 1999-03-03 |
Family
ID=16751051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1220434A Expired - Fee Related JP2863559B2 (en) | 1989-08-29 | 1989-08-29 | Activation method of sulfide precursor type hydrotreating catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2863559B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11164610B1 (en) | 2020-06-05 | 2021-11-02 | Qualcomm Incorporated | Memory device with built-in flexible double redundancy |
| US11177010B1 (en) | 2020-07-13 | 2021-11-16 | Qualcomm Incorporated | Bitcell for data redundancy |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4554350B2 (en) * | 2004-12-24 | 2010-09-29 | 日立建機株式会社 | Gripping force control device and work machine |
| CN104772154A (en) * | 2014-01-15 | 2015-07-15 | 南京大学 | Preparation method of silica supported nickel phosphide catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5319003A (en) * | 1976-08-04 | 1978-02-21 | Mitsubishi Electric Corp | Recording and reproducing system of endless type |
-
1989
- 1989-08-29 JP JP1220434A patent/JP2863559B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5319003A (en) * | 1976-08-04 | 1978-02-21 | Mitsubishi Electric Corp | Recording and reproducing system of endless type |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11164610B1 (en) | 2020-06-05 | 2021-11-02 | Qualcomm Incorporated | Memory device with built-in flexible double redundancy |
| US11640835B2 (en) | 2020-06-05 | 2023-05-02 | Qualcomm Incorporated | Memory device with built-in flexible double redundancy |
| US11177010B1 (en) | 2020-07-13 | 2021-11-16 | Qualcomm Incorporated | Bitcell for data redundancy |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2863559B2 (en) | 1999-03-03 |
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