TW201100167A - Desulphurizing absorbing agent, method for manufacturing the same and application - Google Patents

Abstract

This invention provides an absorbing agent for desulfurization from pyrolysis gasoline and diesel fuel. The absorbing agent comprises the following composition: 1) a carrier composed of silicon oxide source, inorganic oxide binder and at least one metallic oxide selected from a group consisting of IIB, VB and VIB; 2) at least one promoter metal capable of reducing sulfur oxide into hydrogen sulfide in which η is less than 0.5, wherein η = (percentage content of the promoter metal in crystalline phase/percentage content of the promoter metal in chemical composition). Active component in the absorbing agent is uniformly distributed on the carrier to be close to the effect of single layer distribution, whereby greatly increasing the activity of the absorbing agent. This invention also provides a method for preparing the absorbing agent and application.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent for removing sulfur from liquid fuels such as pyrolysis gasoline and diesel oil, and a preparation method thereof. Prior art 〇 〇 With the increasing emphasis on environmental protection 'environmental regulations are becoming stricter', reducing the sulfur content of gasoline and diesel is considered to be the most a & The adverse effects of the converter. The sulfur oxidant present in the exhaust of the automobile engine suppresses the precious metal catalyst in the converter and can cause irreversible poisoning. Gases that are vented from inefficient or poisoned converters contain unburned non-methane L and nitrogen oxides and carbon monoxide, which are readily catalyzed by sunlight to form photochemical smog. Most of the sulfur in China's gasoline comes from hot-processed gasoline, mainly for the release of steam / by 'so the reduction of sulfur content in pyrolysis gasoline helps to reduce

1 'fly / by the sulfur content. China's current gasoline product standard is GB 17930-2006 "straight ra, account, 丄, \, flat oil" 'this standard for the sulfur content of gasoline further

The limit is required to require A to be reduced to 50 ppm in gasoline. Name: Technology μ ^, Under no circumstances, catalytic cracking gasoline must undergo deep desulfurization to meet environmental requirements. In order to maintain the environmentally-friendly quality of the fuel of the car, while reducing the sulfur content of the fuel of the car, the net _ # & Θ should also be used to avoid the change of its olefin content so that it can be used for entertainment. M and MON) are lowered. The negative effect on the olefin content of 201100167 is generally due to the removal of porphin compounds (including porphin, benzophenanthrene, decyl thiophene 'alkyl thiophene and alkyl dibenzothiophene) simultaneously induced nitridation reaction of. In addition, it is also necessary to avoid the conditions that the aromatic hydrocarbons of the pyrolysis gasoline are also lost by saturation, so the most desirable method is to maintain the octane number while achieving desulfurization. On the other hand, both hydrogenation desulfurization and hydrogenation of unsaturated hydrocarbons require the consumption of nitrogen gas, which increases the operating cost of desulfurization. There is therefore a need for a process for desulfurization without significant hydrogen consumption, thereby providing a more economical process for pyrolysis gasoline and diesel fuel processing. Traditionally, desulfurization from a liquid state has often employed a fixed bed method, but the method has obvious disadvantages in terms of reaction uniformity and regeneration. The fluidized bed process has advantages in terms of heat transfer and pressure drop compared with the fixed bed process, and therefore has broad application prospects. The fluidized bed reactor generally employs a granular reactant, and the catalyst particles to be used are required to have sufficient wear resistance. Therefore, it is important to find an adsorbent having good wear resistance and good desulfurization performance. I, 1U093 1A, CN 1 15 1333A provides a novel absorption composition containing an oxidized word, a oxidized oxide, a colloidal oxide, and a promoter, and a method of preparing such an adsorbent. The method uses a pressure forming method to equip the particles of m, and at the same time, the pore volume is increased by adding a porogen which is flammable when heated to the colloid. Us(1) Gang, CN1355727A, CNl help 7ia introduces the adsorbent: contains zinc oxide, oxidized stone, oxidation, reduction valence or knot: mixed 5 sorbent composition; its preparation method is mainly W The emulsified dream, the oxidized zinc and the zinc oxide were mixed and the solid particles were prepared by a granulator 201100167. Both methods were introduced into the active group by the impregnation method. . 422 177 VIII and CN 1627988 Α disclose the impregnation of an adsorbent carrier comprising zinc oxide, permeate perlite and oxidized by using a precursor of a promoter such as nickel, nickel oxide or nickel oxide, followed by the resulting promoter metal The valence of the promoter metal in the sorbent carrier composition is reduced to produce a wear resistant sorbent composition for removing elemental sulphur and sulfides, such as hydrazine, from cracking oils and diesel fuels. And have Ο 化物. The patent (4) comprises a precursor of the promoter metal impregnating the adsorbent carrier to introduce an active component, and the impregnation method has the advantages of simple preparation method and easy implementation, but the degree of homogenization of the promoter metal Often insufficient enough to cause insufficient adsorption desulfurization activity. In this case, in order to increase the activity of adsorption, it is necessary to increase the content of the promoter metal, resulting in an increase in the cost of the adsorbent. SUMMARY OF THE INVENTION The present invention provides an adsorbent for removing ruthenium from pyrolysis gasoline and diesel fuel, wherein the active component in the adsorbent can evenly separate or even approach the effect of monolayer dispersion on the support, thereby greatly increasing the adsorbent. Live for life. The present invention also provides a method of preparing the above adsorbent. The invention also provides for the use of the above adsorbents. The adsorbent provided by the present invention comprises the following composition: 1) a carrier composed of an oxide oxide source, an inorganic oxide binder, and at least one metal oxide selected from the group consisting of ruthenium, VB, and the like; 5 201100167 2 ) at least one capable The promoter metal that reduces the oxidized sulfur to hydrogen sulfide has its η <0·5, where η = the percentage of promoter metal in the crystalline phase / the percentage of promoter metal in the chemical composition. The adsorbent provided by the present invention has a cerium oxide source content of 5% by weight based on the total weight of the adsorbent, a metal oxide content of Μ% by weight, and an inorganic oxide binder content of 3 to 35 as an oxide. The content by weight of the promoter metal is 3 to 3 % by weight based on the oxide. Preferably, the content of the 'cerium oxide source is 1 to 25% by weight, the amount of metal oxide: 40 to 60% by weight, and 10 to 18% by weight of the inorganic oxide binder based on the oxide. The content of the accelerator metal is 5 to 20% by weight. More preferably, the content of the metal as the promoter is 8 to 20% by weight. According to the adsorbent provided by the present invention, the source of the oxidized oxide may be pure oxidized oxide or a mixture containing oxygen, for example, m ( For example: kaolin, layered pillars, etc.), algae, expanded perlite, dream rock, hydrolyzed cerium oxide, macroporous cerium oxide, and a variety of species in Shiqi gum. Examples of the pillared soil include, but are not limited to, rectorite 1 stone, swelling μ, montmorillonite, and smectite. The oxide binder may be one or more selected from the group consisting of alumina, cerium oxide and amorphous lanthanum aluminum oxide. Among them, one or more of γ-alumina-oxidation Ilu is further preferred. The metal oxides of the five children are open-handed handles such as one or more metals of H Β, VB and VIB in the periodic table, or any other metal oxides with sulphur storage properties. Preferably, the oxides of cerium, zinc or a compound of the elements are most preferably oxidized. The promoter metal may be any metal capable of reducing oxidized sulfur to hydrogen sulfide, preferably one or more of nickel, cobalt, manganese, iron, copper, silver, molybdenum, chromium hunger, town and lanthanide metals. It is particularly preferred that the promoter metal contains nickel. In certain embodiments of the invention, η < 〇 5, or even at least one promoter capable of reducing oxidized sulphur to hydrogen sulphide: is a monolayer dispersed on the surface of the support. ❹ ❹ The term "pyrolysis gasoline," which is used to mean 40 to 21 〇t of smoke or any of its contents, is a product from a thermal or catalytic process that cleaves larger hydrocarbon molecules into smaller molecules. Suitable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking cracking, etc., and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluidized bed catalytic cracking and heavy oil catalytic cracking, etc.: combinations thereof. Suitable catalytic pyrolysis gasolines include, but are not limited to, coker gasoline, pyrolysis gasoline, gasoline, fluid catalytic cracked gasoline, and heavy oil pyrolysis gasoline, and combinations thereof. In some cases, the pyrolysis gasoline may be classified and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention. The term "diesel fuel," as used herein, means a liquid consisting of a hydrocarbon mixture of 170 to 45 (rc or any of its constituents. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight run diesel, and Hydrotreated diesel oil, etc., and combinations thereof. The term "琉," as used in the present invention, refers to any form of sulfur element such as a sulfur-containing fluid such as pyrolysis gasoline or an organic sulfur compound commonly found in diesel fuels. The sulfur present in the hydrocarbon-containing fluid of the present invention includes but Not limited to carbon oxysulfide (c〇s), 7 201100167 carbon disulfide (CS2), thiol or other thiophene compounds, and the like, and particularly combinations thereof, including thiophene, benzothiophene, alkylthiophene, alkylbenzothiophene, and alkyl Diphenyl is sold as a thiophene compound having a larger molecular weight which is often present in diesel fuel. The present invention also provides a method for preparing an adsorbent, comprising: (1) making a cerium oxide source, an inorganic oxide binder precursor, and selecting Contacting one or more metal oxides or their precursors in B VB and VIB, forming and drying to form a carrier; (2) placing the carrier in a fluidized bed, An organic compound carried by a gas capable of reducing an oxidized sulfur to a promoter metal of hydrogen sulfide to obtain an adsorbent precursor; &; dry, calcined (2) to obtain an organic compound of a metal for conversion into a metal oxide (4) The adsorbent precursor obtained in (3) is reduced under a reducing atmosphere, so that the promoter metal is substantially present in a reduced state to obtain an adsorbent, and η lt 〇 5 5 ' where η = ^ in the phase The percentage of the promoter metal / the percentage of the promoter metal in the chemical system. In the step (1), the preparation method of the carrier w can be carried out according to the known method, for example, @° A bismuth telluride source, an inorganic oxygenator precursor, and a seed or a multi-oxide or a precursor thereof selected from the group consisting of H Β, and viscous v« and VIB, and water mixed under acidic conditions to be beaten... ~40% by weight of the slurry ': solid carrier., 釭坧, 仔 to microspheres in step (1), oxidized stone scorpion shale (such as: kaolin, .201100167 layer of column dry soil, etc.), Shiyoshizao 'Swelling swelled perlite, enamel, Deoxidizing macroporous cerium oxide and one or more of one of ninth, preferably one or more of expanded perlite, diatomaceous earth and clay. But not limited to rectorite, cloudstone =, ", Examples include preferred rectorites. ^Interstitial, montmorillonite, and montmorillonite, etc., in step (1), the plurality of metals selected from the group consisting of - meaning, from 1], 乂8, and \/^ The oxide or its precursor is a ruthenium of the emulsion itself or an oxide, wherein the precursor of the oxide can be converted into an oxide compound under the preparation of 倏#. For example, a sulfide of one or more metals selected from the group consisting of HB, VB, and the like, a sulfur oxide, a carbonic acid, a citrate, a nitrate, and the like. The gold oxide is preferably an oxide of an element such as vanadium, rhodium or molybdenum, and most preferably zinc oxide. The precursor of the inorganic oxide binder in the step (1) means a substance capable of forming a saturable inorganic oxide during the preparation of the adsorbent. It mainly includes one or several species of oxidized queer, Dong gt; {Bu Shi 々 k + ..., 疋 3L Shi Ximing precursor. For example, the precursor of oxidized Ming may be selected from human ^ β ^ ^ k water σ Oxidation Ming and / or Ming Sol, of which Hydration Oxidation can be selected from - soft water Mingshi (thin water Mingshi), fake one soft water Shaoshi (pseudo-thick water | g stone), two people) one water s emulsified aluminum, amorphous hydrogen One or several of the alumina. The precursor of the oxidized stone cerium may be selected from the group consisting of: shi sol, shixi gel, filial glass, or several. The precursor of the amorphous bismuth aluminum may be selected from the group consisting of 矽 (iv) colloidal sol and (iv) gum mixture 1 (tetra) gum. Precursors of these heat resistant inorganic oxides are well known to those skilled in the art. According to the method provided by the present invention, it is preferred to calcine the carrier of 9 201100167 after drying in step (1), the calcination temperature is 350~7〇〇t, preferably 45〇~650°c, and the calcination time is 1 ~1〇 hours, preferably i~4 hours. In the step (2), the gas is a non-oxidizing gas, preferably an inert gas such as nitrogen, particularly preferably an anhydrous inert gas, and the pressure is from 1 to 5 atm', preferably operated under a usual ink. The temperature of the gas is 5 〇 · (d). . , preferably 50-130. (: In step (2), the promoter metal may be any metal capable of reducing oxidized sulfur to hydrogen sulfide, preferably nickel, cobalt, manganese, iron, copper, silver, lanthanum, lanthanum, hunger, town And one or more of the lanthanide metals, and it is particularly preferred that the promoter metal contains nickel. The organic compound of the promoter metal is selected from organic compounds having a vapor pressure of from 0. 5 to 1 kPa at room temperature (298K). For example, one or more of formate, acetate, metal carbonyl compound and naphthenate. In one embodiment of the invention, the organic compound of the promoter metal uses nickel carbonyl 'specifically nickel tetracarbonyl. (3) wherein the adsorbent precursor is calcined in the presence of oxygen or an oxygen-containing gas at a temperature of from about 300 ° C to 800 ° C, preferably about 45 (rc to 75 ° C, until volatilization) The substance is removed and the promoter metal is converted to a metal oxide. The time required for the calcination is generally from about 5 to about 4 hours, preferably from 1 hour to about 3 hours. In step (4), 'before the adsorbent is used, Reducing the promoter metal under a reducing atmosphere' The promoter metal component of the present invention is obtained in a substantially reduced state (preferably zero valence). The temperature of the reduction reaction is 300 to 600 ° (:, preferably 400 to 500 ° 〇, time is () 5~6 hours, preferably 1~3 hours, the reducing gas content in the reducing atmosphere is 1〇~1 〇〇10.201100167%% The reducing gas is preferably hydrogen, and the remaining gas may be an inert gas such as nitrogen or Argon gas. In the adsorbent obtained in the step (4), η < 〇.5, preferably η = 〇, that is, at least one promoter metal capable of reducing the oxidized sulfur to hydrogen sulfide is substantially monolayer dispersed on the surface of the carrier. The invention also provides a desulfurization method for cracking gasoline or diesel fuel, comprising contacting a sulfur-containing raw material with the adsorbent of the present invention, in which sulfur in the raw material is adsorbed onto the adsorbent, thereby obtaining a product having a low sulfur content. The contact conditions are: temperature 350~5〇(rc, preferably 4〇〇_425.〇, the weight space velocity is 2-81T1, preferably 4_6h-〗, the pressure is 1〇〇〇_5〇〇〇Kpa, Preferably 150()_3〇()() Kpa, the atmosphere is reducing The atmosphere is preferably a hydrogen atmosphere. The adsorbent can be reused after the oxidation-reduction process. 〇 The inventors of the present invention have found that the desulfurization performance of the adsorbent and the effective content of the two-agent metal are large. Relationship: The effective amount of promoter metal refers to the promoter metal that can effectively contact sulfur and adsorb sulfur on the adsorbent: the amount 'before the effective content of the promoter metal reaches a certain value, the adsorption 2 desulfurization performance with the accelerator The metal content increases significantly; when the amount of metal is increased, the desulfurization performance of the adsorbent is improved even if the effective metal content of the H β intercalator is continuously increased. The mass percent of the promoter metal in the phase / the surface of the promoter metal in the chemical group is highly dispersed, /3 liters. If the promoter metal is adsorbed, the promoter metal in the adsorbent does not show a peak in the crystal phase fraction 11 201100167, and its content in the crystal phase composition is 0, that is, η = 0. The η value ilj » ', ' indicates that the metal content of the promoter which is not exposed to sulfur and adsorbs sulfur is less, and the η value can reflect the dispersion of the promoter metal on the surface of the adsorbent, that is, η -〇 indicates that the single layer is dispersed or close to a single Layer dispersion; η > 〇 indicates that the promoter metal is agglomerated, that is, a part of the promoter metal is not in the surface layer and cannot participate in the desulfurization reaction. The larger the value of η, the more the metal content of the promoter in the aggregated state, that is, the greater the metal content of the promoter which is not effectively utilized. Normally, the adsorbent η < 〇·5 prepared according to the present invention, and the adsorbent η > 〇·5 is prepared according to the prior art. The invention adopts the gas phase fluidized bed method to enable the organic compound of the promoter metal to be substantially monolayer dispersed in the surface of the carrier in the fluidized state, and the reduced state obtained after the calcination and reduction treatment (substantially the valence state) The promoter metal is also a monolayer dispersed on the surface of the support. When the amount of the promoter metal is controlled so that the amount of the promoter metal # is the maximum single layer dispersion capacity, the adsorbent has the highest adsorption desulfurization activity. In the case of the same activity, the promoter metal content of the adsorbent of the present invention is lower than that of the prior art by the impregnation method, and the metal content of the promoter is significantly lower, so that the adsorbent can be greatly reduced. ^ JX'j i. Take 0.80 kg of expanded perlite to form an oath of eight q not stone 'C World Mining Company, M27, containing | base 0.79 kg), 0. 71 thousand coupons Gutan - Aling soil (Suzhou Bureau Territory Wei ,S1,乂

Dry base 0.59 kg), oxidation button C Ming h15 kg (Shandong Mingshi produced, including fortunately. 201100167 base 0.78 kg) and 9 〇 kg of acidic water (decationized water, value 3: After mixing evenly under stirring, add ii 〇mL3〇% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) (4) After acidification for 1 hour, add 3.5 kg of oxidized powder and mix for 1 hour to obtain a carrier slurry. The carrier slurry is collected by Niro Bowen Nozzle T〇werTM (4) The spray dryer is spray-dried, the spray dry (four) force is 85 to 9.5 μρ & the inlet temperature is below 〇C, and the outlet temperature is about 150. The micro-ball obtained by spray drying is first at 180 c. Dry for 1 hour, then simmer for 1 hour at 635 〇c to obtain the adsorbent carrier. Place the adsorbent carrier in a fluidized bed. 'Use high purity nitrogen to carry the tetracarbonyl chain (50. After flowing through the adsorbent carrier for 6 hours) The adsorbent carrier after loading nickel is taken out, and then the adsorbent precursor is prepared by burning in an air atmosphere for 65 hours, and the adsorbent precursor is obtained by reducing the precursor of the adsorbent in a nitrogen atmosphere at 425 Torr for 2 hours. The adsorbent It is the adsorbent Αι. The chemical composition of the qi j A1 is μ, the oxonization adhesive is 12.7 wt.%, the expanded perlite is 12 8 (four)%, the kaolin is 9.6 wt.%, and nickel (oxidized). The nickel is calculated to be 8 〇 %. Example 2 The procedure of introducing nickel into the vapor phase adsorption deposition is repeated by using the precursor of the adsorbent A1 instead of the adsorbent carrier, and then it is obtained by baking in an air atmosphere 635 <> The adsorbent precursor and the adsorbent precursor are reduced in a hydrogen atmosphere of 4 丨〇〇c for 4 hours to obtain an adsorbent, and the adsorbent is referred to as A2. The chemical composition of the adsorbent A2 is an oxidized content of M5 wt%, and oxidation is performed. The aluminum binder was 12.1 wt.%, the expanded perlite was 12.3 %, the kaolin 13 201100167 soil was 9.2 wt%, and the _. nickel (calculated as nickel oxide) I 11.9 wt.%. Example 3 Adsorbent Prepared as follows.

Produced by Jinghua Plant) and 4 97... Zinc powder (AT / gram deionized water mixed, then obtained oxidized sulphur slurry. Stir for 30 minutes to take 0.61 kg of diatomaceous earth (Beijing reagent company), 0.96 kg of bar π rf & dry base 0.58 kg) and 5...kg (produced by Shandong Ming Factory, containing dry base 0·82 kg) and 5.0 kg of acidic water (de-yang mixed with Baibo, Ρί1 value of 3) in stirring..._, Into 115 ml of 30% hydrochloric acid (produced by Chemical Industry Co., Ltd.), stir the acidified hydrazine for an hour. , East German Jura, * into the above zinc oxide powder (four) 1 hour passed to the carrier slurry. The carrier solution uses Niro

The Bowen Nozzle ToWerTM spray dryer is spray-dried with a spray drying pressure of 8.5 to 9.5 MPa and a low inlet temperature.

The lower 'outlet temperature is about 15 〇. The microspheres obtained by spray drying are first. Dry under C for an hour' then grab it at 6! The adsorbent carrier was obtained in an hour. The adsorbent carrier was placed in a fluidized bed, and four-base nickel (5 携带 was carried by high-purity ammonia. After flowing through the adsorbent carrier for 6 hours, the adsorbed carrier 1 was taken out after the load was recorded, and then in an air atmosphere 630. The adsorbent precursor can be obtained by 〇c. The adsorbent precursor can be obtained by reducing the adsorbent precursor in a chlorine atmosphere of 4250c for 2 hours, and the adsorbent is recorded as adsorbent A3. The chemical composition of the adsorbent A3 is The zinc oxide content was 57 9 wt%, the alumina binder was 12.7 wt%, the diatomaceous earth was 95 wt%, and the rectorite was ι2·9 14 .201100167 'nickel (calculated as nickel oxide) was 8.0 wt%. Example 1 The preparation method of the first embodiment was prepared by preparing the adsorbent carrier, and immersing 3 24 kg of the adsorbent carrier (dry basis 3. 〇 kg) with 1 〇 3 kg of nickel nitrate hexahydrate, 〇 2 kg deionized water solution After the collapse, the obtained mixture was dried for 18 hours at 18 ° C, and then calcined in an air atmosphere at 635 ° C for 1 hour to obtain an adsorbent precursor. The precursor of the adsorbent was reduced in a hydrogen atmosphere of 425 γ for 2 hours. The adsorbent is obtained, and the adsorbent is referred to as the control agent Bi. The chemical group of the adsorbent B 1 The content of zinc oxide is 57 9 , the alumina binder is 12·7 wt_%, the expanded perlite is 12 8 (10)%, the kaolin is 9_6 Wt.%, and the nickel (calculated as nickel oxide) is 8 〇__%. 2 The adsorbent carrier was prepared according to the preparation method of Example 2. 3 24 kg of adsorbent carrier (dry basis 3.0 kg) was impregnated with 1 〇 3 kg of nickel nitrate hexahydrate 〇 2 kg deionized water solution to obtain a mixture. After drying for 4 hours by i 8 〇 0c ◎, the adsorbent precursor can be prepared by burning in an air atmosphere at 635 ° C for hr. The adsorbent precursor is adsorbed in a hydrogen atmosphere at 425 ° C for 2 hours to obtain adsorption. The adsorbent is recorded as the control agent B2. The chemical composition of the adsorbent B2 is 550% of the oxidized content, the alumina binder is 丨2·1 Wt.%, and the expanded perlite is 12.3 wt.%, kaolin. 9.2 Wt.%, nickel (calculated as nickel oxide) was u 9 %. Comparative Example 3 & makeup method e Preparation Example 3 Preparation of adsorbent carrier. 胄 3.24 kg of adsorbent carrier (dry basis 3· 〇 kilograms) with 61.61 kg of hexahydrate tip acid 15 201100167 nickel, 0.3 kg deionized water solution The obtained mixture was dried over 18 〇〇c for 4 hours, and then fired in an air atmosphere for [hours to obtain an adsorbent precursor. The adsorbent precursor was reduced in a hydrogen atmosphere of 425 ° C for 2 hours to obtain an adsorbent. The adsorbent is referred to as the control agent B3. The chemical composition of the adsorbent B3 is 57 9 wt% of zinc oxide, 12.7 wt.% of alumina binder, 95 wt% of diatomaceous earth, and 129 wt. % 'nickel (calculated as nickel oxide) is 8 〇wt 〇/〇. Example 4 In order to further distinguish the difference between different adsorbents, the crystal phase composition of Al-A3 and B1-B3 was analyzed for the adsorption before reduction. Crystal phase analysis uses χ ray diffraction and phase filtering (R. v. Siriwardane,; A p〇st〇n, g

Evans, Jr. Ind. Eng. Chem. Res. 33 (1994) 2810-2818 ), Modified Rietveld Model (RIQAS rietveld Analysis, Operation Manual,

Material Data, Inc., Berkley, CA (1999)), analyzed different samples, and calculated the crystal phase composition of the sample by fitting method. Using a phiipis XRG3 100 generator equipped with a long thin focus copper and _ ray source driven at 40kV, 30mA; philips 3〇2〇 digital goniometer and phUips 371〇MPD control computer; and Kevex PSI Peltier cooling 矽 detector All X-ray diffraction measurements. Using the Kevex 4601 ion pump controller,

Ke vex 460 8 Peltier power supply, Ke vex 4621 detector bias, Kevex 4561 A pulse processor and Kevex 49 11-A single channel analyzer operate Kevex detector. The diffraction pattern was obtained using Philips APD version 4.1c software. use

Material Data, Inc. Riqas 3 · 1 c version software (Outokumpu HSC 16 201100167

Chemistry for Windows: User Manual, 〇utokumpo Resarch Oy,

Pori, Finland (1999)) performs all rietveld calculations. Intel Pentium Plus IV 2.0GHz class PC with 512MB RAM in MS

Run the program under Windows® 2000 operating system. The crystal phase compositions of the different adsorbents are shown in Table 1. The definition r (Ni = (% Ni in the crystal phase / Ni content in the chemical composition)' is shown in Table 1.

The effective Korean content was analyzed by the H2-TPD method and performed on a Micromerhics Autochem η 292 type adsorption apparatus from the United States. The adsorbent sample was first reduced with hydrogen at 45 ° C for 1 hour and then cooled to room temperature and then purged for 3 G minutes; after purging with high purity nitrogen to the baseline, the temperature was raised to 65 (TC: using thermal conductivity recording颢...~6 丨 出 吸附 吸附 吸附 吸附 。 。 。 。 。 。 。 。 。 。 。 。 吸附 。 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附 吸附As shown in Table 1. ', 〇17 201100167 Table 1 Crystal phase composition of different adsorbents A1 A2 A3 B1 B2 B3 ZnO 64 60 63 58 53 56 ΖηΑ12〇4 17 16 19 19 20 21 Perlite 19 18 - 14 14 - NiO - 5 - 9 13 9 Rectorite - - 21 - - Shixiazao - - - 14 In the crystal phase, Ni hundred 0 0 0 9 13 9 points Chemical composition 8.0 11.9 8.0 8.0 11.9 8.0 Ni percentage effective Nickel content, 7.5 7.6 7.4 4.6 5.5 4.6 wt% ηΝί 0 0.42 0 1.25 1.09 1.25 It is seen from Table 1 that NiO in the adsorbents A1 and A3 is a single layer dispersion and therefore cannot be reflected in the crystal phase composition, ie in the crystal phase. The percentage of N i is 0, then ηΝί is 〇. The ηΝί of the adsorbent A2 is 0.42, indicating The effective Ni content is higher than that of the prior art (the ηΝί of the comparative adsorbents B 1 , B 2 , and B 3 are all greater than 1), and it can be seen from the effective nickel content that the effective nickel content in the adsorbent prepared by the method of the present invention is 7.5. The effective nickel content of the adsorbent prepared by the prior art is not more than 5.5 wt%. 18.201100167 Example 5 The strength of the adsorbent prepared by different methods is evaluated by the straight tube wear method, and the evaluation method thereof Refer to the method of RIPP 29-90 in the "Petrochemical Analysis Method (RIpp) Experimental Method". The results are shown in Table 2. The desulfurization performance of these adsorbents was evaluated by the following method. First, the aging treatment is carried out as follows: the adsorbent is reduced in hydrogen at 420 C 'pressure of 〇·iMpa for 3 hours to contain

The record is restored to zero price. Then, a mixed gas of 10 v〇l.% H2S+ 10 ν〇ι.% H2 + 80 v〇l·% N2 was passed and kept at 420 ° C for 2 hours; a nitrogen human broom was introduced for 5 hours to remove the system. After the hydrogen gas was passed through the air and kept at 5 1 for 2 hours to regenerate the adsorbent. This reduction-sulfidation-oxidation regeneration process was repeated 3 times. The catalytic cracking gasoline was adsorbed at a concentration of 800 ppm by a fixed bed microreaction apparatus. Adsorption test process

The air velocity of the adsorption reaction is determined to be 4 h-!, and the sulfur in the gasoline after the reaction is shown in Table 2. 19 201100167 Table 2 Desulfurization performance of adsorbent Adsorbent raw material A1 A2 A3 B1 B2 B3 Wear strength 9.3 8.8 8.2 9.6 9.3 8.5 Sulfur content of hydrocarbon oil after desulfurization / ppm 800 15 13 15 48 29 51 RON 92.2 91.4 91.2 91.3 91.4 91.3 91.4 MON 81.1 81.1 81.1 81.0 81.0 81.1 81.1 Octane change 0.4 0.5 0.5 0.45 0.45 0.4 Brief description of the diagram Figure 1 shows the XRD patterns of adsorbents A1 and B1. In the same nickel content, Ni in the adsorbent A1 of the present invention is a single layer dispersion, so that substantially, there is a peak of nickel oxide crystal phase, and the adsorbent which promotes R 1 mesh is introduced by the prior art, and the adsorbent of the gentleman % Μ 锦There is a distinct nickel oxide crystal phase peak (characteristic crystal phase peak at 20

Claims (1)

201100167 VII. Scope of Patent Application·· 1 · A desulfurization adsorbent comprising the following components: 1) consisting of a cerium oxide source, an inorganic oxide binder and at least one metal oxide selected from the group consisting of ruthenium, νΒ and shell B a carrier; 2) at least one promoter capable of reducing oxidized sulfur to hydrogen sulfide, η < 〇.5, wherein = percentage of promoter metal in the crystal phase / chemical composition of the promoter metal Sub-content. The adsorbent according to claim 1, wherein the content of the oxidized stone is 1 to 4% by weight based on the total weight of the adsorbent, and the metal oxide content is 10 to 80% by weight/ The content of the inorganic oxide binder in terms of oxide is 3 to 5% by weight, and the content of the promoter metal in terms of oxide is 3 to 30% by weight. The adsorbent according to claim 1 or 2, wherein the content of the cerium oxide source is 1 〇 2 to 25% by weight based on the total weight of the absorbing agent, and the metal oxide content is 40 to 60 The content of the inorganic oxide binder in terms of oxide is 1 Torr to 18% by weight, and the content of the promoter metal in terms of oxide is 5 to 20% by weight. 4. The adsorbent of claim 1, wherein the at least one promoter metal capable of reducing the oxidized sulfur to hydrogen sulfide is substantially monolayer dispersed on the surface of the support. 21 201100167 5. The sorbent agent described in the first paragraph of the patent scope, m, +, 贞, wherein the cerium oxide source is selected from the group consisting of dry soil, Shi Xi sign winter ^ '喿, shaved perlite, enamel rock , hydrolyzed oxidized oxalate, macroporous oxidized stone eve, and one or more of the enamel and enamel. 6. The adsorbent according to claim 1, wherein the inorganic oxide binder is a bismuth aluminum oxide binder. 7 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ One or several. 8. The adsorbent of claim 1, wherein the metal oxide is selected from the group consisting of vanadium, rhodium or molybdenum oxide. The adsorbent according to claim 1, wherein the promoter metal is selected from the group consisting of welding, starting, chaining, arrogant, iron, copper, silver, molybdenum, chromium, vanadium, tungsten and lanthanide metals. One or several. The adsorbent according to the first or eighth aspect of the invention, wherein the promoter metal contains nickel. 11. A method of preparing an adsorbent according to item [i] of the scope of the patent application, comprising: (n a source of cerium oxide, an inorganic oxide binder precursor, and one selected from the group consisting of 22 201100167 HB, VB and νίΒ or A plurality of metal oxides or precursors thereof are contacted, and formed and dried to form a carrier; (2) the carrier is placed in a fluidized bed, and a promoter metal capable of reducing oxidized sulfur to strontium sulfide is carried by a gas. The organic compound obtains the adsorbent precursor; (3) drying and calcining the adsorbent precursor obtained in (2) to convert the organic compound of the promoter metal into a metal oxide; Ο 12 ο 13. 14. () (3) The adsorbent is removed; the promoter is reduced in a reducing atmosphere, and the promoter metal is substantially present in a reduced state to obtain an adsorbent, which has η <0·5, wherein η = promoter in the crystal phase The percentage of the metal / the percentage of the promoter metal in the chemical composition. The preparation method according to the U.S. Patent Application No. U, wherein, in the step (1), the oxygen cutting source is selected from the group consisting of , m, extruded perlite, tannins, One or more of deoxidizing cerium, macroporous cerium oxide, and cerium. The preparation method according to the application of the patent application, wherein, in the step (1), the metal oxide is selected from the group consisting of hunger, Or an oxide of molybdenum, the precursor of the metal oxide being selected from the group consisting of sulfides, sulfates, hydroxides, carbonates, acetates, and nitrates of one or more of the metals of HB, VB, and VIB. The preparation method according to Item 11, wherein in step 23 201100167 (1) φ 'the precursor of the inorganic oxide binder is selected from one or several of the oxidized seconds and the amorphous X-ray aluminum precursor. 5) The preparation method according to the above-mentioned application, wherein in the step (2), the gas is an anhydrous inert gas. 16. The preparation method according to the scope of claim 5, wherein 1), the temperature of the gas is 5 〇 2 2 〇 (rc, the pressure is 7), as described in claim 11, wherein the organic compound of the promoter metal is selected from the group consisting of 298 Torr having a vapor pressure of 100 kpa. Organic compound. The preparation method according to item 17, wherein the organic compound of the promoter metal is selected from the group consisting of nickel, diamond, lanthanum, iron, lanthanum*, crane and lanthanide gold > 1 formic acid M > One or more of the acidity salts. 1 9 _ The preparation method described in claim 11 of the patent, wherein the organic compound of the incoming metal is nickel tetracarbonyl. Self-oxidation I ° , in step, in step 5 Atm ° , the 0.5~, the ferrous, the metal, the metal carbonyl 'the stimuli' in the step to produce 24 1 0, as in the patent application range flute, the preparation method described in item 11, wherein in step (4), Under the original oxygen atmosphere, the promoter metal is reduced, and a metal component which is substantially zero-valent promoter is produced. 201100167 21. The preparation method as claimed in claim 11, wherein at least one of the adsorbents obtained in step (4) is capable of reducing oxidized sulfur. The promoter metal, which is hydrogen sulfide, is substantially monolayer dispersed on the surface of the support. 22. A method for desulfurizing a pyrolysis gasoline or a diesel fuel, comprising contacting a raw material with an adsorbent as described in the scope of claim 2, so that sulfur in the raw material is adsorbed onto the adsorbent, thereby obtaining low sulfur The content of the product. 23. The desulfurization method according to claim 22, wherein the contact condition is: temperature 350 to 5 〇〇 ° C, weight space velocity is 2 to 8 1 T 1, pressure is 1000 to 5000 KPa . 25