WO2001096499A1 - Procede d'utilisation d'un melange de disulfure en tant qu'agent de sulfuration - Google Patents

Procede d'utilisation d'un melange de disulfure en tant qu'agent de sulfuration Download PDF

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Publication number
WO2001096499A1
WO2001096499A1 PCT/KR2000/000606 KR0000606W WO0196499A1 WO 2001096499 A1 WO2001096499 A1 WO 2001096499A1 KR 0000606 W KR0000606 W KR 0000606W WO 0196499 A1 WO0196499 A1 WO 0196499A1
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WO
WIPO (PCT)
Prior art keywords
disulfide
disulfide mixture
mixture
sulfiding
lpg
Prior art date
Application number
PCT/KR2000/000606
Other languages
English (en)
Inventor
Sun Tae Choi
Sung-Jun Lee
Sung-Wook Jang
Kyeong-Hak Seong
Hyun-Khil Shin
Hee-Ju Jung
Jin-Woong Kim
Chun-Young Kim
Original Assignee
Sk Corporation
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 Sk Corporation filed Critical Sk Corporation
Priority to PCT/KR2000/000606 priority Critical patent/WO2001096499A1/fr
Publication of WO2001096499A1 publication Critical patent/WO2001096499A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation

Definitions

  • the present invention relates to a method for preparing a pure disulfide mixture from a by-product produced in an LPG process. Also, the present invention is concerned with use of the pure disulfide mixture as a sulfiding agent useful in oil refining and chemical processes, especially, catalytic desulfurizing processes and ethylene cracking processes.
  • Sulfides suitable for use as sulfiding agents are generally exemplified by dimethyldisulfide, ethyl mercaptan, dimethylsulfide, tetrahydrothiophene, thiophene, diethylsulfide, n-butylmercaptan, and hydrogen sulfide (H 2 S).
  • a catalyst such as CoMo or NiMo, sulfiding agents are decomposed into hydrogen sulfide and adsorbed to allow the catalytic metals to be of reactive activity.
  • sulfide agents are converted into hydrogen sulfide through a thermal cracking mechanism and adsorbed into nickel, which is an active metal for catalytic coking on the surface of the cracking tube, thereby deactivating the coking reaction and lowering the production of carbon monoxide.
  • sulfiding agents should be decomposed into hydrogen sulfide at temperatures as low as possible and be easy to handle safely and to store. Dimethyldisulfide has been prevalent over other sulfiding agents since it best satisfies these requirements (see: Hydrocarbon Engineering Jan./Feb. p. 26, 1987).
  • disulfide mixtures are different in composition from one another in accordance with the type of oil to be treated and process conditions.
  • the disulfide mixtures comprise dimetyldisulfide, diethyldisulfide and ethylmethyldisulfide: these three compounds comprise 98 % or higher of the disulfide compounds produced.
  • dimethyldisulfide has been demonstrated to be an excellent sulfiding agent, and has been used extensively in practice, while there have as yet been no demonstrations of the utility of diethyldisulfide and ethylmethyldisulfide.
  • the disulfide mixtures which are produced as byproducts during an LPG desulfurizing process of oil refineries cause serious pollution of the environment and thus, stand in great need of being utilized.
  • the disulfide mixtures which are produced as by-products during LPG desulfurizing process contain caustic and sodium compounds invariably.
  • the disulfide mixtures containing caustic and sodium compounds exhibit extremely deteriorated catalytic activity.
  • the present inventors developed a method of effectively removing caustic and sodium compounds serving as catalyst poisons from the disulfide mixtures which are produced as by-products during the LPG desulfurizing process of oil refineries and demonstrated through various experimental assay and practical process applications that the remaining disulfide mixtures act as sulfiding agents with similar reactivity to that of dimethylsulfi.de.
  • a method for preparing a sulfiding agent suitable for use in a free sulfiding-required catalytic process comprising the removal step of caustic and sodium compounds from a by-product produced in an LPG desulfurizing process of an oil refinery by washing the by-product with water to give a disulfide mixture and separating the disulfide mixture from the water contained therein.
  • a disulfide mixture as a sulfiding agent suitable in reducing a coking reaction within a cracking tube for an ethylene cracker, wherein the disulfide mixture is prepared by the removal of caustic and sodium compounds from a by-product produced in an LPG desulfurizing process of an oil refinery to give a disulfide mixture.
  • a disulfide mixture is produced, together with a large quantity of caustic and sodium compounds, as a byproduct.
  • the catalyst is greatly deteriorated in the performance thereof owing to the caustic and sodium compounds.
  • a sulfiding agent is prepared from an impurity-free disulfide mixture recovered through a process of washing a disulfide mixture produced in an LPG desulfurizing process with copious water to completely remove caustic and sodium compounds which act as catalyst poisons; and a process of completely removing from the disulfide mixture the water which is present in trace amounts.
  • disulfide compounds preferably amount to at least 98 % by weight.
  • FIG. 1 there is a process flow illustrating the separation of a disulfide mixture from the by-products produced in an LPG desulfurizing process, in accordance with the present invention.
  • a crude LPG is fed into a mercaptan extracting column 1 where sulfur is removed and from which desulfurized LPG is recovered via a separate stream.
  • the by-products produced in this process including a disulfide mixture and caustic and sodium compounds, are transferred through a separator 3 into a washer 4.
  • the washer 4 is structured to be a water wash column. Transferred from the washer 3, the by-products comprising the disulfide mixture and the caustic and sodium compounds are introduced into a lower position of the washer 4. In this connection, washing water is together introduced to effectively conduct the washing of the by-products.
  • the washed disulfide mixture is transferred into a secondary separator 5 from which the water used in the washing is discharged through the lower position of the secondary separator 5.
  • the disulfide mixture is separated from the water contained therein by taking advantage of the difference in their specific gravities. The separation can be performed by sufficiently settling the disulfide mixture. The longer the residence time period in the secondary separator 5 is, the better the separation is. However, a period of several hours to one day is sufficient for the separation.
  • the separation may be conducted in a continuous process or a batch process.
  • the ratio of disulfide mixture to water is in the range of about 6: 1 to 1:2.
  • Fig. 1 is a process flow illustrating the separation of a disulfide mixture from the by-products produced in an LPG desulfurizing process, in accordance with the present invention.
  • disulfide mixtures which were purified of the caustic and sodium compounds in accordance with the separation process illustrated in Fig. 1, were analyzed for physical properties, composition, thermal cracking properties, and catalyst-free sulfiding and reacting performance.
  • Impurities such as caustic and sodium compounds were separated from the by-products of various LPG desulfurizing processes to give disulfide mixtures which were analyzed for their compositions. The results are given in Table 1, below.
  • ethylmethyldisulfide and diethyldisulfide were used for thermal cracking at 470 °C and 530 °C respectively, for the residence time of 2.5 seconds using a micro reactor.
  • the disulfide mixture was tested for free-sulfiding and desulfurizing performance as a free-sulfiding agent.
  • a CoMo/alumina catalyst used in a naptha hydrotreating process, was employed along with a catatester.
  • the temperature condition for free sulfiding was set at 350 °C for the disulfide mixture and the dimethyldisulfide, respectively.
  • the reacting performance of the disulfide mixture was examined over about 70 hours under the same operational conditions as those of a practical process, having a temperature of 300 °C, a reaction pressure of 22 kg/cm 2 , and a sulfide content in reactants of 417 wtppm. The results are given in Table 3, below.
  • This example was also to assay the disulfide mixture for its utility as a free sulfiding agent for a catalytic process. For this, its free sulfiding and desulfurizing reaction performance was evaluated in a pilot plant in the presence of a CoMo/alumina catalyst used for a diesel hydrotreating process. The temperature condition for free sulfiding was set at 280 °C for the disulfide mixture and the dimethyldisulfide, respectively.
  • the disulfide mixture was used as a free sulfiding agent for a kerosene hydrotreating process in the presence of a CoMo/alumina catalyst.
  • the results are given in Table 5, below.
  • the sulfur content of kerosene obtained from the kerosene hydrotreating process was shown to have decreased from 2,200 ppm to 200 ppm or less, which was a similar level to that obtained when dimethyl sulfide was used. From these results, the disulfide mixture was shown to be superior in sulfiding performance.
  • the present invention provides a method with which caustic and sodium compounds can be removed from the by- products produced in an LPG desulfurizing process to prepare a disulfide mixture which is highly suitable for use as a sulfiding agent and applicable for all of the sulfiding processes where conventional sulfiding agents are used.
  • the present invention has many advantages in that the by-products of oil refineries can be converted into a high value-added material through a relatively simple separation operation and the conversion of the by-products is favorable for the environment because the by-products produce pollutants of the air.
  • the present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Abstract

L'invention concerne un procédé de préparation d'un mélange de disulfure pur et d'utilisation dudit mélange en tant qu'agent de sulfuration. Composé essentiellement de diméthyldisulfure, d'éthylméthyldisulfure et de diéthyldisulfure, ledit mélange de disulfure est préparé par élimination des composés caustiques et des composés de sodium d'un sous-produit dans un procédé de désulfuration d'un gaz de pétrole liquéfié (GPL) de raffinerie. Afin d'éliminer lesdits composés, le sous-produit est lavé à l'eau et le mélange de disulfure séparé de l'eau contenu dans ledit mélange. Ledit mélange de disulfure peut être utilisé en tant qu'agent de sulfuration convenant à la réduction d'une réaction de cokéfaction dans un tuyau de craquage pour un craqueur d'éthylène.
PCT/KR2000/000606 2000-06-10 2000-06-10 Procede d'utilisation d'un melange de disulfure en tant qu'agent de sulfuration WO2001096499A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2000/000606 WO2001096499A1 (fr) 2000-06-10 2000-06-10 Procede d'utilisation d'un melange de disulfure en tant qu'agent de sulfuration

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2000/000606 WO2001096499A1 (fr) 2000-06-10 2000-06-10 Procede d'utilisation d'un melange de disulfure en tant qu'agent de sulfuration

Publications (1)

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WO2001096499A1 true WO2001096499A1 (fr) 2001-12-20

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2912757A1 (fr) * 2007-02-20 2008-08-22 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbonne dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
US9353054B2 (en) 2006-12-22 2016-05-31 Arkema France Hydrotreating catalyst sulphiding agent and its use for in situ and ex situ presulphidation
US9562006B2 (en) 2012-08-30 2017-02-07 Arkema France Preparation of symmetrical and asymmetrical disulphides by reactive distillation of mixtures of disulphides
EP3116853A4 (fr) * 2014-03-14 2017-11-15 Reliance Industries Limited Procédé d'élimination du sodium contenu dans une huile disulfure
US10240096B1 (en) * 2017-10-25 2019-03-26 Saudi Arabian Oil Company Integrated process for activating hydroprocessing catalysts with in-situ produced sulfides and disulphides
WO2021236144A1 (fr) * 2020-05-20 2021-11-25 Saudi Arabian Oil Company Conversion de sous-produits de processus mérox en produits utiles dans un procédé de raffinage intégré

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61207489A (ja) * 1985-03-11 1986-09-13 Minoru Matsuda 溶剤で石炭中の有機物を抽出する方法
US4626341A (en) * 1985-12-23 1986-12-02 Uop Inc. Process for mercaptan extraction from olefinic hydrocarbons
KR20000033327A (ko) * 1998-11-23 2000-06-15 남창우 다이설파이드 혼합물을 설파이딩 에이젼트로 사용하는 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61207489A (ja) * 1985-03-11 1986-09-13 Minoru Matsuda 溶剤で石炭中の有機物を抽出する方法
US4626341A (en) * 1985-12-23 1986-12-02 Uop Inc. Process for mercaptan extraction from olefinic hydrocarbons
KR20000033327A (ko) * 1998-11-23 2000-06-15 남창우 다이설파이드 혼합물을 설파이딩 에이젼트로 사용하는 방법

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9353054B2 (en) 2006-12-22 2016-05-31 Arkema France Hydrotreating catalyst sulphiding agent and its use for in situ and ex situ presulphidation
FR2912757A1 (fr) * 2007-02-20 2008-08-22 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbonne dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
WO2008107622A1 (fr) * 2007-02-20 2008-09-12 Arkema France Additif de reduction du cokage et/ou du monoxyde de carbone dans les reacteurs de craquage et les echangeurs thermiques, son utilisation
US8791314B2 (en) 2007-02-20 2014-07-29 Arkema France Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exhangers and use of same
US9562006B2 (en) 2012-08-30 2017-02-07 Arkema France Preparation of symmetrical and asymmetrical disulphides by reactive distillation of mixtures of disulphides
EP3116853A4 (fr) * 2014-03-14 2017-11-15 Reliance Industries Limited Procédé d'élimination du sodium contenu dans une huile disulfure
US10240096B1 (en) * 2017-10-25 2019-03-26 Saudi Arabian Oil Company Integrated process for activating hydroprocessing catalysts with in-situ produced sulfides and disulphides
US10400183B2 (en) 2017-10-25 2019-09-03 Saudi Arabian Oil Company Integrated process for activating hydroprocessing catalysts with in-situ produced sulfides and disulphides
JP2021501232A (ja) * 2017-10-25 2021-01-14 サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ 系中で生成される硫化物および二硫化物で水素化処理触媒を活性させるための統合方法
WO2021236144A1 (fr) * 2020-05-20 2021-11-25 Saudi Arabian Oil Company Conversion de sous-produits de processus mérox en produits utiles dans un procédé de raffinage intégré
US11261386B2 (en) 2020-05-20 2022-03-01 Saudi Arabian Oil Company Conversion of MEROX process by-products to useful products in an integrated refinery process

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