SA109300418B1 - Desulfurizing Adsorbent, Preparation Method and Use Thereof - Google Patents

Abstract

The invention relates to an adsorbent for desulfurization of cracked gasoline or diesel fuel, such an adsorbent comprising: (1) a carrier consisting of a silica source, a binder of inorganic oxides binder, and at least one oxide of a metal selected from Groups IIB, VB, VIB, (ii) at least one accelerant metal capable of reducing sulfur in its oxidized state to hydrogen sulfide and having h < 0.5 where h = (amount in percentage of the accelerant metal in its crystal phase )/ (amount in percentage of the precipitating metal in the chemical composition). The active ingredients can be evenly dispersed on the carrier in a manner close to dispersing in the form of a monolayer, which greatly improves the effectiveness of the adsorbent. The invention also relates to a method of preparation and use of the foregoing adsorbent.

Description

The 0 AA desulfurization adsorbent; Desulfurizing adsorbent, preparation method and use thereof Full description

behind the invention

The invention Jal relates to an adsorbent for desulfurization of liquid fuels such as petrol and diesel

. Cracking gasoline and diesel fuel, which are produced by cracking

With increasing knowledge of the importance of environmental protection; Environmental legislation is gradually becoming more stringent. he thinks that

© Reducing the sulfur content of diesel fuel or diesel gasoline is one of the most important

Measures to improve air quality because the sulfur in the fuel adversely affects the performance of the transformer.

Catalyst for cars and vehicles. The sulfur oxide in the exhaust gases of automobile engines is detrimental

The activity of the noble metal catalyst in the converter and poisoning the catalyst in an irreversible manner. include

Off-gases from a converter that is passive or designed on hydrocarbons other than methane are not 0 combusted; nitrogen oxides » and carbon monoxide » and they all form fumes

Wiles' optical blur when stimulated by sunlight .sunlight

In China; Most of the sulfur in gasolines comes from heat-treated (mainly catalytic) gasoline, which is mainly catalytic cracking ¢ processed gasoline.

cracking gasoline. Therefore, reducing the sulfur content of cracked gasoline will facilitate the reduction of the Vo sulfur content of these gasolines. The current specification for the gasoline product is:

The

D1 -~ (GB 17930-2006 “Motor Vehicle Gasoline,”) which further limits the sulfur content of gasoline and requires that the sulfur content of gasoline be reduced to 0 5 ppm by YY December 1009. This requirement means that cracked benzene must be desulfurized to a significant degree in order to meet environmental requirements.

© When reducing the sulfur content of vehicle fuel, changes in the olefin content that lead to a decrease in the octane number (including the research octane number (ROM) and the engine octane number (MON) must be avoided so that they are kept In general, the negative change in the olefin content occurs through the hydrogenation reaction, which is induced after the removal of thiophene compounds (including benzothiophene (thiophene) « alkylthiophene 0 + alkyldibenzothiophene » 1 s Also, the loss of aromatic hydrocarbons in gasoline produced by cracking due to their saturation under hydrogenation conditions must be avoided.Therefore, the most desirable approach is desulphurization of gasoline while preserving its octane number.From another dal; JS gl Hydrodesulfurization and hydrogenation consume hydrogen, thus increasing the cost of the Vo desulfurization process. Accordingly, there is dala for a method of desulfurization without consuming a large volume of hydrogen, thus saving A more economical way to treat gasoline or diesel fuel

.cracking SAL Producers diesel A fixed bed process is traditionally used for liquid phase desulfurization. However, sale this process is flawed in terms of homogeneity of reaction and matter regeneration. Compared to a fixed bed process; The fluidized bed process is advantageous and has wide applications expected in the future due to Yo

da

Better heat transfer and pressure drop. In this context the “sale” fluidized bed reactor is supplied with granular reactants and the catalyst used requires a particulate material to have sufficient erosion resistance. Accordingly, it is highly important to find an adsorbent that has both excellent erosion resistance and desulfurization performance. The two Chinese patents VN ear and 1513-1 mention a new adsorbent composition comprising zine “silicon dioxide s + oxide”, colloid oxide and an accelerator; and process for making them. In the process fluidizable particles are produced by a pressure-forming method; The particle pore sizes are increased by the addition of a pore-forming substance to the colloid ly which becomes flammable at 0 ASH patent no. A granular adsorbent comprising a mixture of zine oxide, silica precursor, alumina ¢ and nickel or Alla 8 cobalt reduced. The adsorbent is made first by mixing silica source and zine oxides alumina under 348 (al) and preparing solid particles through AT granulation. In these methods nickel is introduced as an active ingredient by impregnation. Vo Chinese patent publications VAIYVAAA and 7719797-11 disclosed an erosion-resistant adsorbent composition prepared by impregnating a carrier of an adsorbent comprising zine oxide, expanded perlite and alumina by using an accelerator such as nickel nickel oxide ¢ or with sala producing nickel oxide ¢ and then reducing the valency of the accelerant metal in the composition of the adsorbent carrier of the resulting accelerant metal. The Yo adsorbent formulation is useful for removing elemental sulfur sulfides ¢ eg hydrogen sulfide YYvo

Organic sulfides from gasoline and diesel fuel produced by cracking. According to these patents, the active ingredient is introduced by impregnating the adsorbent carrier using an accelerant metal containing a precursor; This method of impregnation is beneficial in preparation and easy implementation. However, the precipitated metal introduced in this way does not have sufficient homogeneity; leading to insufficient desulfurization activity in the adsorbent in this situation.”; The amount of metal precipitant used typically increases to enhance the effectiveness of the adsorbent and also increases its manufacturing cost. GENERAL DESCRIPTION OF THE INVENTION The present invention provides an adsorbent for desulfurization of cracked gasoline or diesel fuel. The adsorbent has significantly improved activity. In one embodiment “0 in the adsorbent have active ingredients evenly distributed over the carrier. In another embodiment, the other components are largely distributed in the form of a monolayer over the carrier. The present invention also provides a method for making that adsorbent. The present invention also provides a use for that adsorbent. For example, desulfurization of elemental sulfide from 3 cracking of gasoline and/or diesel fuel. 0 in a practical application; The adsorbent according to the present invention comprises: (0) a carrier comprising a silica source; a binder of inorganic oxides binder and at least aalyoxide of a metal selected from groups VIB. 8 ¢ IIB (Y) at least one accelerant metal capable of reducing the sulfur of

¢ 8 which has a value of converting hydrogen sulfide to oxidized in its oxidized state sulfur parameter "6" is defined as follows: /) crystal phase in its crystal phase accelerant metal (quantity in percentage of accelerant metal =n adsorbent

MN hereinafter; Examples are given of techniques for measuring percentages from which to calculate © The adsorbent provided in this application includes between about 1 and 7450 by weight silica source ; And between about 0 and 280 by weight are metal oxides metal oxides, and between about ? And AYO by weight is a binder of inorganic oxide binder estimated to oxides and between about? and 7270 by weight won accelerant metal Jase is estimated to "oxides"; By weight a metal oxide and between about 01 and 718 by weight a binder of inorganic oxide binder estimated into oxides and between about © and Ye by weight accelerant metal Jaze estimated into oxides ¢ and estimated to the total weight of the adsorbent Vo.It is more preferable that the accelerant metal content range is between about 0 and 4 by weight.ai for the adsorbent provided in this application can be a source of silica either pure silica or a mixture containing 511168; eg one or more kaolin Jie clay baptized clay; etc.); diatomite; expanded perlite ¢ siliceous rock YYVeo

YY = S silica » siliceous rock silica hydrolysis product 3.05 pores 5 silica gel. The inorganic oxide binder in this application is an oxide binder of silica-alumina, which can be chosen from one or more of silica “alumina” and silica-alumina amorphous » alumina ¢ is preferably chosen from one or more alumina — vy + , and — alumina and 0 — alumina ; And

,. alumina - y The metal oxides herein are oxides of one or more metals selected from group 118; oxides of vanadium, or any other metal oxide having sulfur-storing properties; Preferably “VIB 5” and . zinc oxide and the best is zinc or molybdenum

0 The accelerant metal can include any metal Je aE reducing the oxidized sulfur to hydrogen sulfide. It is preferable to choose one or more metals from “manganese “cobalt” nickel, iron, fron, copper, copper, silver, molybdenum, silver, lanthanide, tungsten, vanadium, chromium, and it is better to contain accelerant metal. on -nickel

Yo in some embodiments according to the invention; 1 > 0 ¢ in gyal models 1 = yellow, meaning that at least one accelerant metal is capable of reducing reducing the sulfur in the oxidized state to hydrogen sulfide that is dispersed on the surface of the support material on Mainly monolayer form. must note; that as used in the specification and the accompanying claims; The singular forms "and" and the

‎YYvo

'an' and 'the' include reference to the plural unless the context clearly indicates otherwise. The term 'cracked gasoline' as used in this application means hydrocarbons having boiling ranges between 46 °C and 107 °C or any fractions Some of them are produced by thermal cracking or by catalytic cracking of large hydrocarbons into small particles. Fracking operations included

° suitable temperature; For example but not limited to; pyrolysis 0 thermal cracking 0 viscosity reduction; and combinations thereof. Examples of a suitable catalytic cracking process include; For example but not limited to; Fluidized bed catalytic cracking, heavy oil catalytic cracking, and a combination thereof. Therefore, the suitable product of catalytic cracking gasoline includes, but is not limited to; Coking Gasoline + All Thermal Cracking Gasoline; viscosity-reducing gasoline; Gasoline is the product of heavy oil cracking

0 and combinations thereof. According to the process of the invention, “it is possible in some cases for fractional distillation and/or hydrogenation of benzene as a cracking product before desulfurization when used as a fluid containing 0 hydrocarbons.” The term “diesel fuel” as used in this application means a hydrocarbon mixture. Or any extracts thereof with a boiling range between 11760” C and +40 um. These hydrocarbons contain fluids including but not limited to light re-refined oil; kerosene

Vo » diesel fuel direct distillate; hydrogenated diesel fuel; and combinations of them. sulfurcyg mld means “as used in this application elemental sulfur element sulfur any form; Jie organic sulfide present in a liquid containing Jie hydrocarbons gasoline or diesel fuel two products For cracking, the sulfur contained in a liquid containing hydrocarbons according to the invention includes, but is not limited to:

carbonyl sulfide (COS), carbon disulfide (CS;), mercaptans 0 others; and a combination of them; Especially

The

!a

‎ alkylbenzothiophene 6 alkylthiophene ¢ benzothiophene + thiophene + and its compounds

,. diesel fuel has larger molecular weights usually found in thiophene diesel fuel

The present invention also provides lee for the preparation of an adsorbent comprising the steps: .

inorganic oxide; And a substance that produces a binder of inorganic silica oxide that touches a source of -1. Or materials VIB, VB, 13 ic, and oxides of one or more metals to be selected from a set of 4 binder ©

¢ carrier The molding and drying of the mixture to form a cal carrier

"- Loading the carrier in a fluidized bed; passing a compound containing an organic metal daze

accelerant metal 8.08 reduces oxidized sulfur to hydrogen sulfide, this organic compound

carried by a gas to obtain a precursor to an adsorbent;

1 obtained in the adsorbent step drying and acidification of the material producing the adsorbent (©) 0 oxide; metal accelerant slide so that the organic compound containing the treatment is converted in step 7 ) in a reducing atmosphere so that the adsorbent is reduced by the adsorbent producing substance (€) the accelerator is mainly alone in a reduced state and the adsorbent has a value of < 1, in all there is a crystal phase in its crystal phase accelerant metal (Quantity relative to the metal precipitate = n, where

VO )/ (amount relative to the metal precipitate in the adsorbent). In step (1), the carrier can be prepared according to known methods in this field. For example, “Jaa can make a carrier in the form of fine balls by mixing and whisking a silica source and an inorganic oxide binder.” And oxides of one or more metals to be selected from group 118, VB and VIB. or a precursor and water under acidic conditions;

‎YYVo

Sve by weight solids and then dried about 06 - 01 with about slurry, thus obtaining a slurry by spraying. kaolin clay (i.e. clay from one or more silica clay sources (1) is chosen at step siliceous expanded perlite; expanded perlite baptized diatomite ¢ etc.); clay silica pore 308 silica gel; hydrolysis source; silica; rock© source; Examples of diatomite » expanded perlite preferably one or more expanded perlite » rectorite, Yumeng clay, baptized mentioned include but are not limited to; rectorite clay preferably bentonite, montmorillonite and smectite and VB It may contain one or more metal oxides selected from group 118 and (V) in the oxide-producing step; Where sald) is by itself or oxides by itself or a substance producing it; on the 713 0 oxides that produce oxides are compounds that can be converted into oxides under the preceding conditions of preparation sald) acetates ¢ carbonates + hydroxides + sulfides. Examples of these compounds are the preferred oxides of the phases VIB and VB and one or more of groups 118 and 341 nitrates. zinc oxide and the best “molybdenum or zinc or ¢” vanadium oxide is a substance that can form the inorganic oxide binder (1) in a step; it includes an adsorbent The formation of a heat-resistant inorganic oxide during the process of making the silica adsorbent - and a producing material for a silica source and an alumina source from SST, for example, on one, or it can be alumina, the producing material for (JU) For example, amorphous amorphous hydrated alumina one or hydrated alumina ¢ alumina sol hydrated and/or alumina can be selected from hydroxide © alumina trihydrate ¢ pseudo-boehmite ¢ boehmite more than 00

YYvo

YY = — amorphous aluminum hydroxide . The producing material for the silica source can be chosen from one or more silica gels silica sol and Mayglass ©3781 . The amorphous silica-alumina precursor can be selected from one or more silica-alumina sol ¢ mixtures of silica-alumina gel 5 “alumina sol s silica sol . These refractory inorganic oxides© producers are known to the person of ordinary skill in the art. According to the process of the present invention; It is preferable to roast the dried carrier material after step (1). The roasting temperature ranges between about “You Um” and “Vee”, preferably between about 480 C and 196 C, and the roasting time ranges between about 1 and about 10 Hours, preferably between about 1 hour, in step (7), the gas is a non-oxidizing gas, preferably inert gas, nitrogen Jie ¢ 0, preferably dry inert gas, anhydrous inert gas The pressure of the gas ranges between about 1 and about ¾ atmospheric pressure, preferably atmospheric pressure. Step (1): The accelerant metal can be any metal capable of reducing the oxidized sulfur to hydrogen sulfide, preferably one or more metals chosen from “manganese © cobalt” nickel 0 iron “copper ¢ silver molybdenum 6 silver lanthanide 5 ¢” tungsten ¢ vanadium + chromium 0 and it is better that the accelerant metal contain nickel.The organic compound of the accelerant metal is chosen metal from one or more metal carbonyls ¢ acetates “formates” and naphthenates with a vapor pressure of between about “©,” to about 100 kPa below room temperature (TAA (Kelvin). 0 according to an embodiment of the present invention; The accelerant metal was nickel

11 l

,. Specifically nickel tetracarbonyl » carbonyl

In step (?)” the material producing the adsorbent is calcined between about 00 and about

m preferably between about £00 and about Vor for a period of between about 0,5 and ; hours;

Preferably between about 1 and about T hours in the presence of oxygen or an atmosphere containing oxygen until (A)© the volatiles are completed and the precipitated metals are converted to metal oxide [01618.

in step (4); It is preferable to reduce the precipitating metals in a reducing atmosphere before using the adsorbent

“adsorbent” and thus the precipitate metals are produced in a mainly reduced state (preferably a zero valence);

As well as the adsorbent of the present invention. The reduction temperature is between about Yoo and

Z is about 0101 m, preferably between about 400 “m and about 00 #” m. The time of reduction ranges between

0 is about 8,; f + hours; Preferably between about 1 and about ? hours. amount of reduced gas

between about 01 and 7100 by volume in a reducing atmosphere; Preferably the reducing gas, Je

,. argon or nitrogen gas; The remainder is an inert gas; For example hydrogen gas

The adsorbent obtained in step (4) m 9 ; Rather 0 - yellow

That is, at least one accelerant metal 58 is dispersed on reducing the sulfur 01 in the oxidized state to hydrogen sulfide on the surface of the material

The carrier mainly as a monolayer.

The present invention also provides a method for desulfurizing cracking gasoline or

Diesel fuel is a cracking product that involves full contact of a sulfur-containing substance with a substance

adsorbent according to the invention; During this, the sulfur in the material is adsorbed in the adsorbent, thus obtaining a product with low sulfur.

‎YYvo

— AY - Contact conditions in this regard are as follows: Temperature: between about 0 78 “C and about 0 00” C; preferably between about Ere "C and about 8 C; Gravimetric vacuum velocity: between about 7 and about Tae A preferably between about sf about + Tiel, © pressure: between about 1011 and about 086: 9.9 kPa6 and preferably between about YOu and about oon kilopascals; atmosphere: reduced atmosphere; A thydrogen atmosphere is preferred as the adsorbent can be recycled after passing through a redox regeneration process. Ve the inventor found that the desulfurization property of the adsorbent depends to a large extent on the effective content of the accelerant metal, which means the amount of accelerator metal capable of contacting with sulfur and adsorbing it on the adsorbent. The desulfurization property of the adsorbent increases with the increase in the amount of metal precipitate before the effective content of the metal precipitate reaches a certain value. however; The desulfurization property of the adsorbent cannot be improved even with increasing the amount of metal precipitate after the effective Yo content of the metal precipitate reaches a certain value. =n is defined as (amount in percentage of the metal precipitate in its crystal phase)/ (amount in percentage of the metal precipitate in the adsorbent). If the metal precipitate is largely dispersed on the surface of the adsorbent, then there is no peak corresponding to the metal precipitate in the adsorbent in the analysis of

YYvo

0 = -— crystal phase; Then the quantity is zero, so 0 = zero. the smaller the value of «; The greater the amount of metal accelerator available for contact with sulfur and adsorption. Therefore, 0 indicates the dispersion of the accelerated metal on the surface of the adsorbent. That is, it means the state of dispersion as a monolayer or close to it, where = zero, the precipitating metal begins to agglomerate, and some of it is not found on the surface after that when 0 > zero. the more - the greater; The greater the amount of metal precipitate in the agglomerated state as well. Normally the adsorbent prepared according to the present invention has a = 0.5 7; Whereas the adsorbent prepared according to the prior art .0,# em The fluidized bed method with gas of the present invention can enhance the monolayer dispersion of the organic compound of the metal precipitate on the fluidized surface of the carrier. The metal precipitate Ve is also dispersed on the surface of the support material as a monolayer upon roasting and reduced to the reducing state (HIST (mainly zero). The adsorbent exhibits maximum adsorption efficiency for desulfurization when the amount of metal accelerator used is such that the size of the dispersion of the metal accelerator is the largest aaa monolayer dispersion. The content of the precipitate metal in the adsorbent sald of the present invention is considerably smaller than that input in the material adsorbed by impregnation in the prior art when the same VO exhibits activities; Thus, the production cost of the adsorbent can be greatly reduced. A brief explanation of the libomes shows Figure No. (1) X-ray diffraction models for the two adsorbents (Al (invention) and (Bl) (Gl) above). The Ni metal dispersed as a monolayer 3 mainly adsorbent Al does not show a nickel oxide crystallization peak; While the adsorbent 31 in which the accelerant metal was introduced by the previous art method, y, shows a clear crystallization peak for nickel, YYve |

— ©

.)* 47.5 (characteristic crystallinity peak at oxide

While the forms for the present application are described by reference to the previous forms and the corresponding text and figures; No

The claims are intended to be limited to the models in this description. otherwise;

© The goal is to cover all alternatives, modifications and equivalents found in the content and scope of the models

current content.

A further illustration of the present invention will be made with reference to, but is not limited to, the following examples.

Money No.: (1).

0.860 kg expanded perlite (available from Worldminerals, M27 has a dry weight of 0.4/3 kg); and “YY kg kaolin available from” Suzhou Kaolin CO., SI has a dry weight

4, ; (aa) and 0.19 kg alumina (available from Shandong Aluminum Corporation).

dry weight 0.78 kg); And 9.10 kg acidic water (decationized water

pH *) with stirring, after which 10011 ml of ZY 1101 (pure quality) was added

“Libs are available from (Beijing Chemical Works) and stirred for acidification for 1 hour. After that Vo added 3.5 kg zine oxide powder; mixed and stirred for 1 hour to obtain

Slurry slurry is a carrier.

The slurry was spray dried using a Niro Bowen Nozzle Tower™ spray dryer.

at a pressure between 8.8 and 4.0 MPa” and an inlet temperature of less than 0000”C and a temperature of

The outlet is about 050” C. The fine spheres obtained by this method were dried at 8380 C.

‎YYvo

= 011 — for 1 hour; Then it was calcined at 175"C for 1 hour to obtain a carrier for the adsorbent. The adsorbent carrier was loaded into a fluidized bed; highly affinity nitrogen gas carrying 01 (nickel tetracarbonyl "m) for + hours. Then the adsorbent carrier loaded with nickel was taken out and roasted in air at 7156°C for 1 hour to produce an adsorbent precursor. The adsorbent precursor was reduced ad a hydrogen atmosphere at 4720”C for 2 hours to produce an adsorbent; reported as the adsorbent AT the adsorbent AM consisted of 781.9 wt” zine oxide 217.7 wt binder alumina 0 » 2178 by weight expanded perlite 1 expanded perlite 74.7 by weight kaolin and 78.0 by weight nickel (as nickel acid). By vapor deposition of the adsorbent with the replacement of the adsorbent carrier by the adsorbent precursor ay adsorbent Al that A Vo roasting the precursor of the adsorbent at © 17 "m in air for 1 hour to produce the adsorbent producing material; which was reduced at 10 m for 1 hours to produce an adsorbent; dda sale 707,79 wt alumina expanded perlite + 74,7 wt kaolin » and 711,4 YYvVe

197 -

.) nickel oxide) nickel by weight

Example No. (7)

The adsorbent was prepared as follows: 0.¥ kg zinc oxide powder (available from Beijing) was mixed

(Chemical Works) and €,4Y kg deionized water 0 and then stirred for To minutes to obtain

,. zinc oxide from slurry on slurry ©

0.11 kg diatomite (available from Beijing Chemical Reagent Co., Ltd. dry weight) was mixed

54 kg) 5 55 kg rectorite (available from Qilu Petrochemical Catalyst Company » to him

Ae ala weight + kg) alumina (from Shandong Aluminum Corporation) has a basic weight

(aS “AY) and 0.0 kg acidic cla (dehydrated water; pH) with 0 stirring and then 115 mL 770 HCI (pure quality Lila) was added. Available from Beijing

(Chemical Works) with stirring to acidify for 1 hour. After that powder was added

zine oxide previous”; and mixed and stirred for 1 hour to obtain a slurry as a carrier

Niro Bowen Nozzle Tower™ by spraying with a spray dryer slurry The slurry has dried. carrier

spray; at a pressure between AO and 5.59 MPa” and an inlet temperature of less than n+20) and 0 outlet temperature was about 100”C. The microspheres thus obtained were dried

at 8560 m for 1 hour; And then roasted at 5 ?+”C for 1 hour to get a substance

A carrier of the adsorbent.

The adsorbent carrier was loaded into a fluidized bed; Je

Me nitrogen purity holds B70) nickel tetracarbonyl for > hours. Then the nickel-laden adsorbent carrier Ye was taken out and calcined in air at 0015m for 1

‎YYve

#1 — hour to produce an adsorbent precursor. The adsorbent precursor was reduced under an atmosphere of hydrogen at 476 “C for 2 hours to produce an adsorbent; it is reported as adsorbent 3e. Adsorbent A3 consists of 789.9 by weight zinc oxide » and 717.7 alumina binder © E, 79.8 by weight diatomite, 717.9 by weight pillared clay + 78.0 by weight nickel nickel oxide Comparative example 1 The material was prepared Adsorbent carrier according to the method of example (1) with the following differences. 4 7.7 kg of adsorbent carrier (Led) dry weight 7.0 kg) were impregnated using VF 0 kg of nickel nitrate hexahydrate and 1.7 kg of deionized water 061001260. The mixture then obtained in this way was dried at a YA for 1 hour and calcined in air at 1 m for 1 hour to obtain a precursor for the adsorbent. The precursor for the adsorbent was reduced under an atmosphere of hydrogen at 475 "C for two hours to produce a precursor and then gy J was reported as Bl VO Adsorbent 31 consisted of 757, 9 wt. 17.7 zinc oxide 7 wt. alumina binder ¢ 17.8 wt. expanded perlite » 74.6 wt. kaolin » and 0.78 wt. nickel nickel oxide! )) Comparative example ( ) Y YYVo

19- The adsorbent carrier was prepared according to the method of example (7) with the following differences. 4 3.7 kg of the adsorbent carrier (having a dry weight Te kg) were impregnated with O kg of nickel nitrate hexahydrate ¥, + kg of deionized water The obtained mixture was dried In this way at 0180 pm for ; hours; and roasted in air at 178"C for 1 hour to obtain an adsorbent precursor. The adsorbent was reduced under an atmosphere of hydrogen at 75"C for 2 hours to yield an adsorbent reported as B2 The B2 adsorbent consists of 754.4 by weight 17.1 by weight zine oxide 7 by weight sale alumina bond + 717.9 by weight expanded perlite » 24.7 by weight kaolin ¢ and 0,711.5 by weight (nickel oxide) nickel (. Comparative example (7) The adsorbent ied carrier was prepared according to the method of example (3) with the following differences. 7.74 kg of the adsorbent (having a weight of Yoo Gla kg) was impregnated with 11.1 kg of 1.7 nickel nitrate hexahydrate kg deionized water. The mixture obtained in this way was VO titrated at VAY for ; hours; And roasting it in air at 2710 sad 1 hours to get a sale yielding the adsorbent. Then reduction of the adsorbent yielding adsorbent was induced by an atmosphere of hydrogen at 759 mm for 2 hours to produce an adsorbent reported as 33. Adsorbent 83 consisted of 757,4 by weight 1,7 zine oxide 7 wt sale YYvo Association

1e — alumina » 74.0 wt. diatomite + 717.4 wt. rectorite; And 778.0 by weight, nickel (shiny nickel). Example No. (4) in order to distinguish between the previous different adsorbents; The crystal phase compositions of the adsorbed gall of © pre-reduced AL-A3 and 31-83 were measured and the “values” were calculated. The crystal phase was analyzed using X-ray diffraction and phase filtering: (R. 101 Siriwardane, J.

A.

Poston, 6. Evans, Jr.

Ind.

Eng.

Chem.

Res. 33 (1994). All X-ray diffraction measurements taken using a Philips XRG 3100 alse equipped with a long fine focus copper X-ray source operated at 50 kV Fo mA, a Philips 3020 digital goniometer and a Philips control computer 3710 MPD 01 + Kevex PSI Peltier Coolant Silicon Detector. Kevex Detector 1 driven by Kevex Ion Pump Controller; Kevex 4608 Current Supply “Kevex 4621 Detector Bias and Kevex Pulse Processor 4561A » Single Channel Analyzer - 4911 Kevex A YYvo

- 1? Diffraction patterns were obtained using Philips APD version 4.02 software. All Outokumpu (from Material Data, Inc. 181085 version) were performed using p3.1 Rietveld calculations.

HSC Chemistry for Windows: Users Guide, Outokumpo Research Oy, Pori, Finland ) (1999) Programs were run under MS Windows® 2000 using an Intel Pentium® IV 2.0GHz © PC © 11 MB The compositions of the crystalline phase of the different samples are shown in Table No. (1). Definition of “= (the percentage of Ni in the crystalline phase / the percentage of 1 in the adsorbent). It was analyzed The effective content of 14 by the 117-100 method measured on the Autochem H 2920 0 adsorption apparatus from ... 0 Micromeritics The adsorbent samples were reduced by hydrogen gas at 580 um for an hour and cooled cleaned to atmospheric temperature for 10 minutes; then cleaned with le Np purity to reach a constant baseline; finally heated to 186 a until then } signals were recorded by a thermal conductivity detector and the amount of hydrogen adsorbed was calculated by 0 apex area, then calculate the amount of Ni adsorbed with hydrogen atoms, i.e. effective nickel content depending on the relationship that one hydrogen atom was adsorbed by a nickel atom. The mentioned results are shown in Table No. (1).

YY - - — Table No. (1): Crystal phase compositions for different adsorbents. 9 1 9 Crystal phase Percentage of 141 in Mr 14 A, M 7 A, 15 Chemical composition: Effective nickel content » / L 7,1 7 71 ed by weight [fe] We are a as Seen in Table No. (1); it is 1810 in Al and A3 adsorbents in a monolayer ¢ and thus cannot be reflected in the composition of the crystalline phase, meaning that the percentage of Ni in the crystalline phase is equal to zero then my = zero The adsorbent 2m has a wed = 0.7 which indicates that the effective nickel content is greater than in the previous art ny) for the comparative adsorbents BL, 2 and 83 are greater than Sar 1) Also from the active content note that “the adsorbents according to the present invention have an effective content of about 77.5 by weight; While the adsorbent materials according to the previous art shall not exceed 70.0 by weight of the active nickel content. D 75

??-

Ho number example).

The strength of the adsorbents prepared by different methods was evaluated by tube erosion method

my head; This method can be referred to method 18100-90-29 in:

“Analysis in petrochemicals, RIPP test methods” The results mentioned in Table (7) were recorded. The following methods were used to evaluate the desulfurization performance using these adsorbents.

0.1 bia at nitrogen of s” under the adsorbent adsorbent sald) reduced: citlab

megapascals and at a temperature of Fad SEY hours until all the nickel in the

the adsorbent to a valence of zero. Next a gas mixture of 711 vol 11.5 + 700 vol was passed through

Hy + 780 by volume and through the adsorbate kept at 10 7; "m sad 2 hours. The cleaning was done with 0 and a saucer to remove the hydrogen of the system for 0.8 hours, after which air was introduced to the Ball

The adsorbent was kept at 105"C for two hours to reactivate it. The reactivation process was repeated. Reduction - sulfation

Oxidate this three times.

A fixed bed microreactor was used to evaluate the desulfurization performance. ‎Joli sale Adsorption is a term

Al mainly catalytic cracking gasoline The sulfur content Ave Vo is ppm. The adsorption test was carried out under nitrogen atmosphere at vacuum and gravimetric velocity.

.)( The sulfur content of benzene is recorded in Table No. del

‎YYve

—- Ys Table No. (7): Desulfurization performance of adsorbent materials Adsorbent material

B3 B2 Bl A3 A2 Al adsorbent Benzene Hydrocarbon Sulfur Content 511 Yq $A Yo 01 0 Ae After Desulfurization (ppm) Al YYVo

Claims (1)

Gather the protections 1 1 - An adsorbent for removing sulfur, which includes: (1) Y is a carrier consisting of _ from a source of sale “silica bond” of inorganic oxides binder ~~ ¥ and at least one oxide of metal chosen; From groups VIB (VB ¢ IIB E (v) an accelerant metal, at least one capable of reducing sulfur, sulfur 1, in its oxidized state, to hydrogen sulfide, and has a value of 1 > 0.5, where = n 1 (Amount in percentage of the accelerant metal in its crystal phase) / (Amount in percentage of the accelerant metal in the adsorbent 1) adsorbent 1 * - The adsorbent according to Claim No. (1), where the adsorbent includes between about 1 and 7490 by weight source 511:68; and between about 0 and Ae By weight metal oxides metal oxides and between about ?and 778 by weight sale bond - from an inorganic oxide binder estimated to oxides and between about ©?and JY. The accelerant metal is estimated to be “oxides” estimated to the total 1 weight of the adsorbent 0 adsorbent 1 * - The adsorbent according to Claim No. (1), where the adsorbent Y includes between about 0 and 7780 by weight silica source and between about 8 and Ihe v by weight metal oxides metal oxides » and between about 0 and VA by weight sale bond; - from an inorganic oxide binder estimated to oxides and between about © #5 and 770 by weight Accelerant metal Determined to oxides Determined to total ‎YYVo _Y=—_ 1 Weight of the adsorbent. 1 ¢ - The adsorbent Lai adsorbent of claim No. (1); where the metal accelerator 7 of the base (at least one accelerant capable of reducing sulfur 26006108) is in ¥ in an oxidized state to Hydrogen sulfide is dispersed on the surface of the support material in the form of a monolayer. silica of claim (1); where the adsorbent source is selected adsorbent - *# 1; expanded perlite rock » diatomite; clay from one or more clays ¥ silica source « hydrolysis silica; A siliceous rock source F. silica gel 5; large pores 1 1 - the adsorbent as, adsorbent of protection element No. 1 1, where the inorganic oxide binder Y is a sale of the oxide binder of L oxide silica-alumina. V 1 - The adsorbent according to the two claims (1), where the binding material is selected from Y inorganic oxide binder 016h:100 from one or more alumina ¢ sources? silica and silica-alumina are 0 amorphous 1 / - The adsorbent according to the claim (1) where the metal oxide is chosen from vanadium oxide Y, zinc or molybdenum. YYvo yy one accelerant metal where the accelerant metal (1) is an adsorbent material according to the claim — © 1 silver “copper ¢ iron” manganese + cobalt nickel or more than 0 with clip 1 “tungsten” vanadium “chromium 0” molybdenum according to claim (1), where the adsorbent metal adsorbent - 3 01 nickel includes accelerant metal ~~ ¥ It includes the steps: (V) Adsorbed according to claim sole Process for the preparation of - 11 1 inorganic oxide; and a substance producing a silica inorganic oxide binder in contact with (1) v source or VIB and VB precursor and IIB, the oxides of one or more metals selected from the group of binder ¥ its carrier, and molding and drying of the mixture to form a carrier; d (i) loading the carrier into a fluidized bed and passing an organic compound containing A metal accelerator carrying the compound hydrogen sulfide capable of reducing oxidized sulfur to the aforementioned organic accelerant metal on a gas to obtain an adsorbent precursor; V obtained in the step of adsorbent drying and acidification of the adsorbent precursor (©) + metal into accelerant metal oxides? So that the organic compound of the accelerator metal is converted 4 oxides 0 treatment in a step (©) in a reductive adsorbent atmosphere Reducing the substance produced for the adsorbent (£) 11 mainly in a reduced state by itself and to be accelerant metal so that the metal is present VY accelerant (amount in percentage of metal accelerator =m where © + adsorbent nN of the adsorbent VY accelerant (amount in percentage of metal accelerant crystal phase metal 01.) adsorbent for bottom In the adsorbent 0 YYvo ( \ ) in step silica J) wherein the source of ' (11) method is selected according to claim No. -10 rock ¢ expanded perlite; perlite expanded diatomite » clay from one or more 7" silica clays; source of hydrolysis All silica source 511166015 silicone rock Y. silica gel; large-pore" oxide of where The metal oxide is selected from +1 0) of claim number laa Method - 1 ¢ vanadium, zinc or molybdenum ¥ ¢ hydroxides « sulfates ¢ sulfides Selection of the material producing metal oxides from phy ¥ .nitrates s + acetates carbonates ¢ The method according to Claim No. (11), whereby the material producing the binder is selected from VE-1 alumina from one or more of (1) in an inorganic oxide binder step 0 amorphous crystalline silica-alumina; and a precursor of silica source + ¥ is gas (Y) where the gas is in step “(11) of the method according to Claim No. 11 1 0 anhydrous inert gas “ala inert ¥ where the gas temperature ranges between about 6 and (11) for protection number fa, method = 1 1 and the gas pressure ranges between about or © atmospheric. 5 Yoo ¥ YYVo —_ Y 8 m 17 1 - The method according to Claim No. (VY), where the organic compound containing x accelerant metal is selected from organic compounds having a vapor pressure ranging between about 0 + 011 yy kPa at 7978 m CALS YAY - the method according to Claim No. (VY) where the organic compound containing the accelerant metal is selected from one or more acetates « formates ¢ metal compounds « manganese ¢ cobalt » naphthenates nickel 5 « carbonyls iron fron ¢ copper copper; ¢ silver 0 lanthanide 5 « tungsten » vanadium ¢ chromium « molybdenum + silver 19 1 - The method according to claim No. (11), where the organic compound containing accelerant metal is -nickel tetracarbonyl accelerant metal 0 (VY) of claim number la, method - Ye 1 is reduced, and thus an accelerator metal component is produced in a zero valency state in the form of (Jide) from step (€) in an atmosphere Y 0 major 7 accelerant metal Jase where a metal is dispersed »(11) method according to Claim No. 1 - 1 oxidized Alla 8 reducing the sulfur at least one capable of reducing sulfur Y obtained in step An adsorbent present in the hydrogen sulfide adsorbent mainly to ¥ monolayer (;) on the surface of the carrier as a monolayer; diesel fuel desulfurizing cracking gasoline A method for desulfurizing gasoline fuel - YY 1 what Y Two products by cracking include the contact of the sulfur-containing material with an adsorbent according to the element > protection (1) and during this the sulfur contained in the material is adsorbed in the adsorbent, thus obtaining a product with a low sulfur content. YY 1 - method according to claim (77); wherein the contact conditions are: “temperature between about You” m and about 018 um; YF gravimetric vacuum velocity between about “Y hours” and about 8 hours' ; pressure between about 0001 kPa and about 5000 kPa. M7