WO2000067897A1 - Desulfurant de produits sulfures organiques par adsorption et son procede de preparation - Google Patents

Desulfurant de produits sulfures organiques par adsorption et son procede de preparation Download PDF

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Publication number
WO2000067897A1
WO2000067897A1 PCT/CN1999/000152 CN9900152W WO0067897A1 WO 2000067897 A1 WO2000067897 A1 WO 2000067897A1 CN 9900152 W CN9900152 W CN 9900152W WO 0067897 A1 WO0067897 A1 WO 0067897A1
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WO
WIPO (PCT)
Prior art keywords
molecular sieve
exchange
type
modification
preparation
Prior art date
Application number
PCT/CN1999/000152
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English (en)
Chinese (zh)
Inventor
Jie Zhang
Ke Lin
Zhenyi Liu
Original Assignee
Jie Zhang
Ke Lin
Zhenyi Liu
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 Jie Zhang, Ke Lin, Zhenyi Liu filed Critical Jie Zhang
Priority to AU59655/99A priority Critical patent/AU5965599A/en
Publication of WO2000067897A1 publication Critical patent/WO2000067897A1/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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity

Definitions

  • the invention relates to an adsorbent desulfurizing agent for organic compounds and a preparation method thereof, in particular to a molecular sieve type adsorbing desulfurizer for finely removing organic compounds in liquid hydrocarbons and a preparation method thereof.
  • Organic compounds include alcohol, , Phenol, oxygen carbon, carbon disulfide, thiophene, etc .; the currently used hydrodesulfurization method only converts the thiol compounds in the hydrocarbon to H 2 S, and then removes them by other methods.
  • Catalytic oxidation method is to convert mercaptans into odorless diethyl ether, di-ether etc. Extraction with liquid agent, but the accuracy of desulfurization can not meet the requirements of low sulfur in raw materials.
  • U.S. Patent No. 4,204,947 describes a method for fine alcohol removal, which is not only used at high temperatures and harsh regeneration conditions, but also can only remove mercaptans, and is incapable of other forms of organic sulfur.
  • Chinese patent CN 8510355.5A describes an iron-manganese-zinc-based desulfurizer. Although it has the advantage of a wide range of organic sulfur removal, the desulfurization activity temperature is greater than 350 ° C. It is not possible for hydrocarbons that are not suitable for desulfurization by this method. use. The H 2 S product also exists in the hydrolysis conversion method, which needs to be removed by other methods.
  • Molecular sieves have many uses in physical, physical chemistry, and chemical processes, and are most suitable as selective adsorbents, to complete the separation of components in mixtures, and as catalysts.
  • the use of molecular sieves to remove H 2 S and mercaptans from natural gas has been used in some applications. Since most of the commercially available molecular sieves are sodium molecular sieves, their adsorption capacity is low, which requires frequent regeneration, which increases desulfurization. The cost of operation is very difficult for industrial application. Disclosure of invention
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and provide an adsorption desulfurizing agent for organic sulfide with large adsorption capacity, high removal accuracy, and long regeneration period, and a preparation method thereof.
  • a further object of the present invention is to provide a modified molecular sieve type adsorption desulfurizing agent capable of finely removing organic sulfides in liquid hydrocarbons, and a method for preparing a molecular weight sieve modified desulfurizing agent using high-valent lanthanide metal cation .
  • An adsorption desulfurizing agent for finely removing organic sulfides in liquid hydrocarbons The main component of the adsorption desulfurizing agent is an X-type or Y-type molecular sieve modified by a high-valent metal cation.
  • the silicon-to-aluminum ratio of the Y-type molecular sieve is 3.0 to 5.0; the silicon-to-aluminum ratio of the X-type molecular sieve is 2.2 to 3.0;
  • the metal cation used for the modification is a high-valence La series cation, such as Sc 3 + , Y 3 + , La 3+ , Ce 3 + , Sm 3 +, Eu 3 +, Tb 3 + or mixed rare earth cations; the metal cation used for modification is La 3 + or Ce 3 + or a mixture of the two, so
  • the shape of the finished product of the desulfurizing agent is spherical or cylindrical or sheet-shaped or clover-shaped.
  • a method for preparing an organic sulfide adsorption degrading agent includes the following steps: a. Selecting X-type or Y-type molecular sieve raw powder; b. Preparing an aqueous solution of a high-valent La-type metal cation with a concentration of 0.05 to 1 mol / L as a solution Exchange solution or mixed rare earth cation aqueous solution; c. Adopt ion exchange method to perform ion exchange modification on the molecular sieve with the ion exchange solution in step b above; d, dry the modified molecular sieve powder and add an appropriate amount of binder Forming granulation.
  • the concentration of the exchange liquid in the step b is 0.05 to 0.1 mol L.
  • the metal cations used for the modification are high-valent La-based cations, such as Sc 3 + , Y 3 + , La 3+ , Ce 3 +, Sm 3 + , Eu 3 + or mixed rare earth cation aqueous solution.
  • the metal cation used for the modification is La 3 + or Ce 3 + or a mixture of both, and La 3 + having a positive trivalent is particularly preferred.
  • Modification of molecular sieves is carried out by atmospheric pressure ion exchange and exchange and roasting; modification of molecular sieves can also use high pressure ion exchange; modification of molecular sieves can also use continuous ion exchange; modification of molecular sieves can also use isomorphous substitution ;
  • the above-mentioned various ion exchange methods require an exchange degree of more than 82%.
  • the applicant overcomes the shortcomings of low adsorption capacity, and proposes to modify the molecular sieves by using high-valent metal cations, so that the local position within the molecular sieve channels can increase the strength of the electrostatic field, and make hydrocarbons in the logistics
  • the sulfur atoms in the sulfide are polarized and adsorbed (the sulfur atoms are much more electronegative than carbon atoms), so the sulfide adsorption capacity is greatly improved.
  • the desulfurization precision is high, the sulfur capacity is large, the regeneration cycle is extended, and the production cost and operation cost are greatly reduced. The best way to implement the invention
  • the metal cations selected in the present invention are: Sc 3+ , V 3+ , Y 3+ , La 3+ , Ce 3+ , Sm 3+ , En 3+ > Tb 3+ , mixed rare earth and the like.
  • the selected molecular sieves are commonly used products such as X-type and Y-type.
  • the silicon-aluminum ratio of X-type molecular sieve is 2.2 to 3.0, and the silicon-aluminum ratio of Y-type molecular sieve is 3.0 to 5.0.
  • the modification method adopts 1 atmospheric pressure ion exchange method, that is, the metal to be exchanged is prepared into a nitrate or hydrochloride, and the nitrate or hydrochloride is made into a 0.05-l mol / L aqueous solution, preferably 0.05 to 0.1 mol / L.
  • concentration of L In order to improve the degree of exchange, an intermittent multiple exchange method or a continuous exchange method can be used.
  • the multiple-exchange method involves filtering, washing, drying, and high-temperature roasting of molecules after one exchange, and then performing a second exchange, so as to repeat the exchange multiple times until the desired degree of exchange is reached. Exchange and high-temperature roasting are carried out, which can improve the degree of exchange and exchange efficiency.
  • a molecular sieve is packed in a packed column, and the metal salt solution is continuously passed for exchange until the degree of exchange reaches the required requirements.
  • the high-pressure ion exchange method that is, the ion exchange is performed in a closed system, and the temperature can be increased to about 150-300 ° C, which can strengthen the exchange process and improve the degree of exchange and exchange efficiency.
  • 3 Modification can also use the well-known isomorph substitution method.
  • Molecular sieve should be X-type molecular sieve. Compared with X-type and Y-type molecular sieve, X-type molecular sieve has a lower silicon-aluminum ratio, and more cations can be exchanged than ⁇ -type molecular sieve. X-type molecular sieve exchanged up There are more high-valent cations than Y-type, so the adsorption capacity of the modified X molecular sieve is larger than that of ⁇ -type molecular sieve.
  • La 3+ is preferred as the exchange ion.
  • the molecular sieve after La 3+ ion exchange has the strongest polarity, so the adsorption capacity is large.
  • the exchange degree is required to be greater than 82% after the exchange.
  • the modified molecular sieve is further processed into a spherical, cylindrical, sheet or clover-shaped desulfurization adsorbent with the required mechanical strength.
  • an appropriate amount of a binder such as sheep glycyrrhizin can be added to the modified molecular sieve powder, and the amount of addition is not more than 30% (wt) of the total weight of the desulfurizing agent.
  • Atmospheric pressure Weigh out a certain amount of X-type molecular sieve raw powder, put it in a 500ml mill-mouth three-use bottle, pour 250ml 0.05 ⁇ 0.1 mol / L of a high-value soluble metal salt solution, and heat and reflux in an electric furnace for 4 hours After cooling, it is filtered, washed, and dried, and then baked at 550 ° C for 2 to 4 hours, so that the exchange rate reaches 82%.
  • the evaluation test of the test desulfurization agent was performed in a pressure evaluation device.
  • the diameter of the reaction tube was 13 mm
  • the particle size of the desulfurization agent was 40 mesh
  • the loading amount was 10 ml.
  • Test conditions a space velocity, 2111; temperature, 20 ⁇ 25. C; pressure, 10 Kgf / cm 2 .
  • Analytical instrument Microcoulometer (minimum detection amount 0.2ppm).
  • Experimental raw materials Mixed carbon four from a refinery was used, with a total sulfur content of 40 ppm, of which the H 2 S content was 3 ppm.
  • the composition of organic sulfur is: CH 3 SH, CH 3 CH 2 SH, C 3 3 ⁇ 4S, C H10S, , C5H12S, C2H6S2, C5H12S, C3H8S2, C H14S, C 7 H 16 S, C 4 H 10 S 2 , C 2 3 ⁇ 4S 3 , C 4 H 7 NS, C 5 H 12 S 2 .
  • C 2 3 ⁇ 4S 2 > 72%
  • C 3 H 8 S 2 > 8% C 2 S 3 > 14%, and the rest ⁇ 6%.
  • the evaluation test mainly examines the comparison of the removal effect of different modified samples with unmodified X-type and Y-type molecular sieves and the effect of regeneration on the dehutting effect of the desiccant. During the test, when If the presence of sulfur is detected by the mouth, the deoxidizing agent is considered to have penetrated, and at this time, the volume is penetrated and sparse. The test results are shown in Table 1.
  • the modified molecular sieve has a 5- to 10-fold increase in sulfur capacity at a time compared to the original powder of X-type or ⁇ -type molecular sieve.
  • the invention relates to a molecular sieve type adsorption desulfurizing agent for finely removing organic sulfides in liquid hydrocarbons and a preparation method thereof.
  • the main component of the adsorption desulfurizing agent is an X-type or Y-type molecular sieve modified by a high-valent metal cation.
  • the desulfurizer can be widely used to remove organics from various kinds of sulfur-containing materials such as liquid hydrocarbons, steam, coal, and diesel. It has been confirmed by industrial experiments that its permeation sulfur capacity is greater than 1.5 to 2.5% (wt), which can be repeatedly regenerated more than 1,000 times. It has the characteristics of high accuracy, large sulfur capacity, long regeneration period, and long life of desulfurizer. Can greatly reduce production costs and operating costs.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un désulfurant par adsorption à tamis moléculaire servant à éliminer les produits sulfurés organiques contenus dans des hydrocarbures à l'état liquide et le procédé de préparation de ce désulfurant. Ce désulfurant est essentiellement constitué d'un tamis moléculaire de type X ou Y modifié par un cation du métal de lanthanide à forte valence. Le tamis moléculaire de type X présente un rapport silicium-aluminium allant de 2,2 à 3 et le tamis moléculaire de type Y fait preuve d'un rapport silicium-aluminium allant de 3 à 5. Le désulfurant d'adsorption de cette invention fait preuve d'une forte sélectivité, d'une grande capacité d'adsorption, d'un niveau élevé de désulfuration et peut être utilisé plusieurs fois grâce à son long cycle de régénération.
PCT/CN1999/000152 1999-05-11 1999-09-24 Desulfurant de produits sulfures organiques par adsorption et son procede de preparation WO2000067897A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU59655/99A AU5965599A (en) 1999-05-11 1999-09-24 Adsorbing desulfurizer for removal of organic sulfides and methods of making them

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN99107219.7 1999-05-11
CN99107219 1999-05-11

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Publication Number Publication Date
WO2000067897A1 true WO2000067897A1 (fr) 2000-11-16

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PCT/CN1999/000152 WO2000067897A1 (fr) 1999-05-11 1999-09-24 Desulfurant de produits sulfures organiques par adsorption et son procede de preparation
PCT/CN2000/000109 WO2000067898A1 (fr) 1999-05-11 2000-05-11 Desulfurants a tamis moleculaire et son procede de preparation

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003103176A (ja) * 2001-09-28 2003-04-08 Nippon Oil Corp 炭化水素用脱硫触媒、脱硫方法および燃料電池システム

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60333129D1 (de) * 2003-06-06 2010-08-05 Zeochem Ag Verfahren zur entfernung von schwefelverbindungen aus verunreinigtem gas und flüssigkeitsströmen
CN112958166A (zh) * 2021-03-15 2021-06-15 常州大学 一种分子筛离子交换的方法及其分子筛离子交换系统
CN113083226A (zh) * 2021-03-16 2021-07-09 湖北工程学院 纳米载铜活性分子筛的制备方法及变压器油的处理方法

Citations (2)

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Publication number Priority date Publication date Assignee Title
US5057473A (en) * 1990-04-12 1991-10-15 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Regenerative Cu La zeolite supported desulfurizing sorbents
US5146039A (en) * 1988-07-23 1992-09-08 Huels Aktiengesellschaft Process for low level desulfurization of hydrocarbons

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US4383916A (en) * 1981-08-28 1983-05-17 Standard Oil Company (Indiana) Sweetening and desulfurizing sulfur-containing hydrocarbon streams
US4376103A (en) * 1981-10-26 1983-03-08 Standard Oil Company (Indiana) Removing sulfur oxides from a gas
CN1026225C (zh) * 1991-02-28 1994-10-19 中国石油化工总公司石油化工科学研究院 一种稀土y分子筛的制备方法
CN1069553C (zh) * 1997-11-25 2001-08-15 中国石油化工总公司 一种制备稀土y型分子筛的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5146039A (en) * 1988-07-23 1992-09-08 Huels Aktiengesellschaft Process for low level desulfurization of hydrocarbons
US5057473A (en) * 1990-04-12 1991-10-15 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Regenerative Cu La zeolite supported desulfurizing sorbents

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003103176A (ja) * 2001-09-28 2003-04-08 Nippon Oil Corp 炭化水素用脱硫触媒、脱硫方法および燃料電池システム
JP4559676B2 (ja) * 2001-09-28 2010-10-13 Ｊｘ日鉱日石エネルギー株式会社 炭化水素用脱硫触媒、脱硫方法および燃料電池システム

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AU5965599A (en) 2000-11-21
AU4534000A (en) 2000-11-21
WO2000067898A1 (fr) 2000-11-16

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