WO2000067898A1 - Desulfurants a tamis moleculaire et son procede de preparation - Google Patents

Desulfurants a tamis moleculaire et son procede de preparation Download PDF

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Publication number
WO2000067898A1
WO2000067898A1 PCT/CN2000/000109 CN0000109W WO0067898A1 WO 2000067898 A1 WO2000067898 A1 WO 2000067898A1 CN 0000109 W CN0000109 W CN 0000109W WO 0067898 A1 WO0067898 A1 WO 0067898A1
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WO
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Prior art keywords
exchange
molecular sieve
type
degree
valent metal
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PCT/CN2000/000109
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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 AU45340/00A priority Critical patent/AU4534000A/en
Publication of WO2000067898A1 publication Critical patent/WO2000067898A1/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 a molecular sieve type desulfurizing agent for removing organic sulfur compounds in liquefied petroleum gas or light oil products, and a preparation method thereof.
  • Sulfur in petrochemical products can be divided into organic sulfur and inorganic sulfur.
  • Inorganic sulfur is mainly hydrogen sulfide, which can be easily removed using different desulfurizing agents and corresponding desulfurization processes.
  • Organic stone fillings include thiol polar organic phosphants and non-polar organic sulfides (or neutral organic sulfides) such as thioether, thiophenol, thiocarbon, carbon disulfide, and thiophene; currently used to remove organic sulfur
  • the methods include hydrodesulfurization method and catalytic oxidation method.
  • the hydrodesulfurization method is to remove the above-mentioned organic ⁇ L in a hydrocarbon oil (including liquefied petroleum gas, naphtha, catalytic gasoline, aviation kerosene, kerosene, diesel oil) by converting it into an inorganic sulfide, which is relatively expensive.
  • the catalytic oxidation method converts mercaptans into odorless thioethers, disulfides, etc., and extracts them with solvents.
  • the US patent US 4204947 introduces a method for fine mercaptan removal, which not only uses high temperature 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. Such a high desulfurization temperature is suitable for the desulfurization of hydrocarbons. It cannot be used.
  • Molecules have many uses in physical, physical chemistry, and chemical processes, and are most suitable as selective adsorbents to complete the separation of components in a mixture and as a catalyst.
  • the use of X-type molecular sieves to remove H 2 S and mercaptans from natural gas has been applied, but it cannot be used to remove neutral organic sulfides.
  • U.S. Patent No. 5,146,039 proposes a method for removing low-content sulfides in hydrocarbons using a cation-modified molecular sieve.
  • the molecular sieve used in this method uses copper, silver, and zinc as modified cations of type A, X, or Y molecular sieves.
  • US5057473 proposes a renewable molecular sieve carrier desulfurization adsorbent, using copper and lanthanum as modified cations of 13X molecular sieve, the contact time for ion exchange is 24 and 48 hours, and the temperature of ion exchange is room temperature and 75 ⁇ 80 ° C, the molecular sieve obtained after the exchange is used to remove the total ⁇ L of flowing hydrocarbons including hydrogen, in the experiment of removing the fuel of the internal combustion engine at a temperature of about 250 ° C, after 1 An hour's reflux can remove 60% of the total sulfur; this desorbent uses a chemical adsorption method when removing stone gangue, and a corresponding oxidative regeneration method during regeneration, so the regeneration is complicated and the service life is short. Disclosure of invention
  • the purpose of the present invention is to provide a molecular sieve desulfurizing agent for directly removing organic sulfur compounds in liquefied petroleum gas or light oil by physical adsorption method with large adsorption capacity, high removal rate, convenient regeneration and long life in use. And its preparation method.
  • the purpose of the present invention is to provide a molecular sieve desulfurizing agent for directly removing organic sulfide in liquefied petroleum gas or light oil by physical adsorption method with large adsorption capacity, high removal rate, convenient regeneration and long life in use.
  • the technical solution is:
  • the molecular sieve desulfurizing agent of the present invention is mainly composed of X-type or Y-type molecular sieves modified with high-valent metal cations, and is characterized in that the elements of high-valent metal cations are lanthanum, cerium or mixed light rare earth Element, the degree of exchange of high-valent metal cations is 70% to 95%.
  • the degree of exchange of the high-valent metal cations of the modified X-type molecular sieve is 82% to 95%.
  • the degree of exchange of the high-valent metal cations of the modified X-type molecular sieve is preferably 82% to 86%.
  • the degree of exchange of high-valent metal cations of the modified Y-type molecular sieve is 70% to 75%.
  • the degree of exchange of the high-valent metal cations of the modified Y-type molecular sieve is preferably 70% to 73.5%.
  • the shape of the finished product of the above-mentioned desulfurizing agent is spherical or cylindrical or sheet-shaped or clover-shaped.
  • the purpose of the present invention is to provide a method for directly removing organic matter from liquefied petroleum gas or light oil by physical adsorption method with large adsorption capacity, high removal rate, convenient regeneration and long life in use.
  • the technical scheme of the method for preparing sulfide molecular sieve desulfurizing agent is as follows: 1 Use X-type or Y-type molecular sieve raw powder; 2 Prepare lanthanum, cerium or mixed light rare earth elements with a concentration of 0.05 ⁇ 0.2mol / l An aqueous solution of high-valent metal cations is used as an exchange liquid. 3 The ion exchange method is used to ion-exchange the original molecular sieve powder with an exchange solution until the exchange-modified high-valent metal cations have an exchange rate of 70% to 95%.
  • the molecular sieve powder used in the above method is X-type raw powder; the ion exchange method is a reflux type atmospheric pressure ion exchange method, and the reflux time is 2 to 6 hours; the exchanged molecular sieve powder is filtered, dried, roasted, and roasted The time is 2-4 hours, and the roasting temperature is 450 ⁇ 500 ° C.
  • the ion exchange method is used for the second exchange modification, so that the degree of exchange of high-valent metal cations of the modified X-type molecular sieve reaches 82% to 86%. .
  • the exchange modification and roasting are performed alternately, so that the degree of exchange of high-valent metal cations of the modified X-type molecular sieve can reach 86% to 95%.
  • the molecular sieve powder used in the above method is a Y-type raw powder; the ion exchange method is a reflux type atmospheric pressure ion exchange method, and the reflux time is 2 to 6 hours; the exchanged molecular sieve powder is filtered, baked, roasted, and roasted The time is 2-4 hours, and the roasting temperature is 450 ⁇ 550 ° C; the roasted molecular sieve powder is cooled and placed in the above-mentioned exchange liquid, and the second exchange modification is performed by using the above-mentioned reflux type atmospheric pressure ion exchange method, so that
  • the modified Y-type molecular sieve has a high-valent metal cation exchange degree of 70% to 73.5%.
  • the exchange modification and roasting are performed alternately, so that the exchange degree of the high-valent metal cations of the modified Y-type molecular sieve can reach 73.6% to 75%.
  • the ion exchange method used in the above method is a high pressure ion exchange method.
  • the exchange temperature is maintained at 150 ⁇ 300 ° C in a high pressure vessel, and the exchange time is> 3 ⁇ 4 hours, so that the degree of exchange of high-valent metal cations reaches 70% to 95%. .
  • the molecular sieve raw powder used in the above-mentioned high-pressure ion exchange method is X-type raw powder, and the exchange time is 3 to 4 hours, so that the degree of exchange of high-valent metal cations reaches 82% to 86%.
  • the molecular sieve raw powder used in the above-mentioned high-pressure ion exchange method is X-type raw powder, and the exchange time is longer than 3 to 4 hours, so that the degree of exchange of high-valent metal cations reaches 86% to 95%.
  • the molecular sieve raw powder used in the above-mentioned high-pressure ion exchange method is a Y-type raw powder, and the exchange time is 3 to 4 hours, so that the degree of exchange of high-valent metal cations reaches 70% to 73.5%.
  • the original molecular sieve powder used in the above-mentioned high-pressure ion exchange method is a Y-type original powder, which has a large exchange time. Within 3 to 4 hours, the degree of exchange of high-valent metal cations can reach 73.6% to 75%.
  • the ion exchange method used in the above method is a continuous atmospheric pressure ion exchange method, which allows the exchange solution to flow from top to bottom through a fixed bed filled with molecular sieve raw powder.
  • the fixed bed temperature is 85 to 95 ° C and the time is 3 to 10 days. , So that the degree of exchange of high-valent metal cations reaches 70% to 86%.
  • the molecular sieve raw powder used in the continuous atmospheric pressure ion exchange method is an X-type raw powder, and the degree of exchange of high-valent metal cations is 82% to 86%.
  • the original molecular sieve powder used in the above-mentioned continuous atmospheric pressure ion exchange method is a Y-type original powder, and the degree of exchange of high-valent metal cations is 70% to 73.5%.
  • the preferred concentration of the exchange solution in the above method is 0.05 to 0.09 mol / l.
  • the present invention has positive effects: (1) Based on the characteristics of molecular sieves capable of physical adsorption, in order to overcome the shortcomings of low adsorption capacity for neutral organic sulfides, on the one hand, the present invention uses high-valent rare earth metal cations to modify molecular sieves. It can increase the strength of the electrostatic field at the local position in the molecular sieve channels, and make the neutral sulfide molecules in the hydrocarbon stream polarized and easily adsorbed. Therefore, the adsorption capacity and adsorption efficiency of organic sulfides are greatly improved.
  • the control and selection of the rare earth metal cations with a high valence state for the degree of exchange of sodium ions to> 70% and also greatly improve the adsorption capacity and efficiency of molecular sieves for neutral organic sulfides.
  • the molecular sieve of the present invention is suitable for large-capacity physical adsorption and desorption of organic sulfur, especially neutral organic sulfides, after application, the desulfurization rate is high, the sulfur capacity is large, the regeneration cycle is long, and the regeneration The process is also relatively convenient, thereby greatly reducing production costs and operating costs, and making industrial applications possible.
  • the desulfurizing agent of the present invention can be widely used for removing organic sulfur from sulfur-containing hydrocarbon oils such as liquefied petroleum gas, gasoline, kerosene, and diesel oil. It has been verified by industrial practice that its permeation sulfur capacity is greater than 1.5 to 2.5% by weight, and it can be repeatedly regenerated more than 1,000 times. (3) Because the present invention solves the bottleneck problem in the prior art that the molecular sieve technology, which has a small sulfur capacity or a short service life, restricts the industrialization of neutral organic sulfide applications in the refining industry; therefore, the present invention Popularization and application will greatly improve the quality of hydrocarbon oil products (also known as oil products), in order to meet the emerging new social needs and environmental protection requirements.
  • hydrocarbon oil products also known as oil products
  • the rare earth metal to be exchanged is prepared into a nitrate or a hydrochloride, and the nitrate or the hydrochloride is made into an aqueous solution as an exchange liquid, and the concentration of the exchange liquid is
  • the concentration is 0.05 to 0.2 mol / L, preferably 0.05 to 0.09 mol / L.
  • the modification method adopts 1 reflux type atmospheric pressure ion exchange method: X-type or Y-type molecular sieve is repeatedly refluxed in the exchange solution, and filtered after one exchange. Wash, dry, roast at high temperature, and then perform the second exchange, and then repeat the exchange many times until the desired exchange degree is reached. Exchange and high-temperature roasting are performed alternately, which can improve the degree of exchange and exchange efficiency.
  • the exchanged molecular sieve powder is cooled, taken out, filtered, washed, and dried, and baked at a high temperature of 490 ° C for 2 to 4 hours to obtain a finished product eight.
  • the rest is the same as in Example 1, except that the exchange solution is a 0.1 mol / L cerium nitrate solution, and the exchange rate of cerium reaches 85% to obtain a finished product B.
  • the exchange solution is 0.15 mol / L mixed lightly diluted Soil nitrate solution to obtain the finished product C with a mixed light rare earth cation exchange rate of 82.5%.
  • the mixed light rare earth is produced by the rare earth plant of Baotou Iron and Steel Company.
  • lanthanum nitrate accounts for about 50%
  • cerium nitrate accounts for about 45%
  • thorium nitrate accounts for about 0.175%.
  • the finished product A, B or C obtained through the two-pass two-bake method of the above embodiments 1 to 3 can be pressed again or multiple times. The same process is performed for exchange and baking until a finished product with the required degree of exchange is obtained.
  • Example 4 The rest is the same as in Example 4, except that the exchange solution is a 0.1 mol / L cerium nitrate solution, and the exchange rate of cerium reaches 72%, and a finished product 5 is obtained.
  • the exchange solution is a 0.1 mol / L cerium nitrate solution, and the exchange rate of cerium reaches 72%, and a finished product 5 is obtained.
  • the rest is the same as in Example 4, except that the exchange solution is a mixed light rare earth nitrate solution of 0.15 mol / L, and a finished product F having a mixed light rare earth cation exchange degree of 70.5% is obtained.
  • the mixed light rare earth is produced by the rare earth plant of Baotou Iron and Steel Company.
  • lanthanum nitrate accounts for about 50%
  • cerium nitrate accounts for about 45%
  • thorium nitrate accounts for about 0.175%.
  • the finished product D, E, or F obtained by the two-pass two-bake method in the above embodiments 4 to 6 can be pressed again or multiple times. The same process is carried out for exchange and roasting, until a mouthful of exchange rate is obtained.
  • the molecular sieve should be preferably 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 Y-type molecular sieve. The X-type molecular sieve exchanges more high-valent cations than the Y-type, so the adsorption capacity of the modified X-type molecular sieve is larger than that of the Y-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 of the X-type molecular sieve is required to be> 82%, and the exchange degree of the Y-type molecular sieve is required to be> 70%.
  • 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 may 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.
  • the evaluation test of the test desulfurizing agent was performed in a pressure evaluation device.
  • the diameter of the reaction tube was 13 mm
  • the particle size of the desulfurizing agent was 40 mesh
  • the loading amount was 10 ml.
  • Test conditions Airspeed: 2h; Temperature: 20 ⁇ 25 ° C; Pressure: 10 Kgf / cm 2 .
  • Analytical instrument Microcoulometer (minimum detection amount 0.2ppm).
  • the evaluation test mainly examines the comparison of the desulfurization effect between different modified samples and the unmodified X-type and Y-type molecular sieves, and the effect of regeneration on the desulfurization effect of the desulfurizer. During the test, when sulfur is detected at the outlet, the desulfurizing agent is considered to have penetrated, and the sulfur capacity at this time is the penetrating sulfur capacity.
  • the modified molecular sieve has a 5- to 10-fold higher sulfur capacity than the original powder of X-type or Y-type molecular sieve.
  • Regeneration experiment Samples A, B, C, D, E, F, G, and H containing stone grams were regenerated with a high-temperature nitrogen purge at 300 ° C.
  • the regeneration space velocity was 500 h " 1 , and the stones were removed after 50 regenerations.
  • the gram efficiency is still more than 95% of the initial state.
  • the present invention relates to a molecular sieve type adsorbing and removing agent for finely removing organic sulfides in liquid hydrocarbons, and Its preparation method.
  • the main components of the adsorption desulfurizing agent are modified by high-valent metal cations.
  • the remover can be widely used to remove organic sulfur from various 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 desulfurization accuracy, large capacity, long regeneration period, and long life of desulfurizer, which can greatly reduce Production costs and operating expenses.

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

Abstract

L'invention concerne un désulfurant à tamis moléculaire destiné à éliminer les produits organiques sulfurés d'un gaz de pétrole liquide ou de produits pétroliers bruts ainsi que le procédé de préparation de cet agent désulfurant qui est essentiellement constitué d'un tamis moléculaire de type X ou Y modifié par un lanthane, un cérium ou un élément de terres rares léger mélangé à forte valence. Le taux d'échange des cations métalliques à forte valence oscille entre 70 et 95 %. Ce désulfurant s'applique directement pour éliminer des composés sulfurés organiques neutres contenus dans le gaz de pétrole liquide et les produits pétroliers légers par adsorption physique. Ce désulfurant fait preuve d'une forte d'absorption, d'un long cycle de régénération, d'une régénération aisée, d'une longue durée de vie et peut être réutilisé.
PCT/CN2000/000109 1999-05-11 2000-05-11 Desulfurants a tamis moleculaire et son procede de preparation WO2000067898A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU45340/00A AU4534000A (en) 1999-05-11 2000-05-11 Molecular sieve desulfurizers and methods of making them

Applications Claiming Priority (2)

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

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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 (4)

* 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
WO2004108273A1 (fr) * 2003-06-06 2004-12-16 Zeochem Ag Procede d'elimination de composes soufres de flux liquides et gazeux contamines
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 (4)

* Cited by examiner, † Cited by third party
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US4376103A (en) * 1981-10-26 1983-03-08 Standard Oil Company (Indiana) Removing sulfur oxides from a gas
US4383916A (en) * 1981-08-28 1983-05-17 Standard Oil Company (Indiana) Sweetening and desulfurizing sulfur-containing hydrocarbon streams
CN1053808A (zh) * 1991-02-28 1991-08-14 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
CN1220188A (zh) * 1997-11-25 1999-06-23 中国石油化工总公司 一种制备稀土y型分子筛的方法

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
DE3825169A1 (de) * 1988-07-23 1990-02-01 Huels Chemische Werke Ag Verfahren zur feinentschwefelung von kohlenwasserstoffen
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN1053808A (zh) * 1991-02-28 1991-08-14 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
CN1220188A (zh) * 1997-11-25 1999-06-23 中国石油化工总公司 一种制备稀土y型分子筛的方法

Cited By (5)

* 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
WO2004108273A1 (fr) * 2003-06-06 2004-12-16 Zeochem Ag Procede d'elimination de composes soufres de flux liquides et gazeux contamines
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

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AU5965599A (en) 2000-11-21
AU4534000A (en) 2000-11-21

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