RU2393919C2 - Desulphuration and novel desulphuration method - Google Patents

Desulphuration and novel desulphuration method Download PDF

Info

Publication number
RU2393919C2
RU2393919C2 RU2007108545/04A RU2007108545A RU2393919C2 RU 2393919 C2 RU2393919 C2 RU 2393919C2 RU 2007108545/04 A RU2007108545/04 A RU 2007108545/04A RU 2007108545 A RU2007108545 A RU 2007108545A RU 2393919 C2 RU2393919 C2 RU 2393919C2
Authority
RU
Russia
Prior art keywords
composition
mixture
method according
form
sulfur
Prior art date
Application number
RU2007108545/04A
Other languages
Russian (ru)
Other versions
RU2007108545A (en
Inventor
Тусхар В. ЧАУДХАРИ (US)
Тусхар В. ЧАУДХАРИ
Гленн В. ДОДВЕЛЛ (US)
Гленн В. ДОДВЕЛЛ
Марвин М. ДЖОНСОН (US)
Марвин М. ДЖОНСОН
Дебора К. ДЖАСТ (US)
Дебора К. ДЖАСТ
Original Assignee
Конокофиллипс Компани
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
Priority to US10/914,798 priority Critical patent/US20050020446A1/en
Priority to US10/914,798 priority
Application filed by Конокофиллипс Компани filed Critical Конокофиллипс Компани
Publication of RU2007108545A publication Critical patent/RU2007108545A/en
Application granted granted Critical
Publication of RU2393919C2 publication Critical patent/RU2393919C2/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8603Removing sulfur compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3078Thermal treatment, e.g. calcining or pyrolizing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/104Alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/112Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/24Hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/304Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/306Organic sulfur compounds, e.g. mercaptans
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/308Carbonoxysulfide COS
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/40Further details for adsorption processes and devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42Materials comprising a mixture of inorganic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/104Light gasoline having a boiling range of about 20 - 100 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1048Middle distillates
    • C10G2300/1055Diesel having a boiling range of about 230 - 330 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70Catalyst aspects
    • C10G2300/703Activation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04Diesel oil

Abstract

FIELD: chemistry.
SUBSTANCE: present invention relates to removal of sulphur from hydrocarbon streams, to a composition which is suitable for use in desulphuration of streams of cracked petrol and diesel fuel, and a method of preparing the said composition. A method of preparing a composition for removing sulphur from hydrocarbon streams involving the following is described: (a) mixing: 1) a liquid, 2) first metal formate, 3) material containing silicon dioxide, 4) aluminium oxide and 5) second metal formate, to form a mixture of the said components; (b) drying the said mixture to form a dried mixture; (c) calcination of the dried mixture; and (d) reduction of the calcined mixture with a reducing agent under reduction conditions to form a composition which contains a low valency activator, (e) separation of the obtained composition, where the said calcined reduced mixture facilitates removal of sulphur from a stream of hydrocarbons under desulphuration conditions, and where the said liquid is ammonia, and the composition obtained using the method described above. A method of removing sulphur from a stream of hydrocarbons involving the following is described: (a) bringing the stream of hydrocarbons into contact with the composition obtained using the method described above in a desulphuration zone under conditions which facilitate formation of a desulphurated stream of hydrocarbons from the said sulphonated composition and formation of a separate desulphurated stream of hydrocarbons and a separate sulphonated composition; (c) regeneration of at least a portion of the said separate sulphonated composition in the regeneration zone to remove at least a portion of sulphur contained in it and/or on it and formation of a regenerated composition as a result, (d) reduction of the said regenerated composition in an activation zone to form a composition containing a low valency activator which facilitates removal of sulphur from the stream of hydrocarbons when it touches such a composition, and e) subsequent return of at least a portion of the said reduced composition to the said desulphuration zone. Cracked petrol and diesel fuel obtained using the method described above are described.
EFFECT: more stable removal of sulphur from streams of hydrocarbons during desulphuration.
26 cl, 8 tbl, 17 ex

Description

This invention relates to the removal of sulfur from hydrocarbon streams. In another aspect, this invention relates to compositions suitable for use in the desulfurization of cracked gasoline and diesel fuel streams. Another aspect of this invention relates to methods for making compositions for use in removing sulfur impurities from cracked gasoline and diesel streams.

The need for more complete combustion of fuel led to ongoing ongoing worldwide efforts to reduce the level of sulfur in the flow of hydrocarbons, such as gasoline and diesel fuel. Reducing the sulfur content in such hydrocarbon streams is considered as a means of improving the quality of the air environment due to the fact that sulfur has a negative impact on the performance of its sensitive components, such as catalytic afterburners of automobile exhaust gases. The presence of sulfur oxides in the exhaust of an automobile engine inhibits and can irreversibly poison noble metal catalysts found in the exhaust gas afterburner. Emissions from an ineffective or poisoned exhaust gas afterburner contain unburned residues, non-methane hydrocarbons, nitrogen oxides and carbon monoxide. Such emissions are catalyzed by sunlight and form a surface ozone layer, commonly called smog.

Heat-treated gasolines, such as, for example, thermal cracking gasoline, visbreaking gasoline, coking gasoline and catalytic cracking gasoline (for which the term “cracking gasoline” is used collectively), contain some olefins, aromatics, sulfur and sulfur-containing compounds. Since most gasolines, such as motor gasolines, gasoline for racing cars, aviation gasolines, gasolines for ships, etc., contain cracked gasoline as a component, at least in some quantities, a reduction in the sulfur content of the gasoline cracked It will naturally help to reduce the sulfur content in most types of gasoline, such as, for example, automobile gasoline, gasoline for racing cars, aviation gasoline, gasoline for ships, etc.

The public debate on the sulfur content of gasoline did not focus on whether or not the sulfur content should be reduced. The general opinion was that reducing the sulfur content in gasoline reduces the emission of automobile exhaust gases and improves the quality of the air. Accordingly, the standards to date have focused on the required level of decline, the geographic areas that require low sulfur gasoline, and the time frame for meeting the requirements.

As there remains a problem regarding the impact of automobiles on air pollution, it is clear that additional efforts will be required to reduce the sulfur content in automotive fuels. While gasoline currently contains approximately 330 ppm sulfur (ppm), the U.S. Environmental Protection Agency recently issued a directive requiring the average sulfur content of gasoline to be less than 30 ppm on average with an upper limit of 80 ppm By 2008, the standards will actually require that every gasoline sold in the United States meets a 30 ppm sulfur content.

In addition to the need to make it possible to produce low-sulfur automotive fuels, there is also a need for a method that will have a minimal effect on the olefin content of such a fuel so that its octane number is maintained (both the research-type octane and octane number according to the motor method). Such a method would be desirable since the saturation of olefins significantly affects the octane number. Such an adverse effect on the olefin content is usually caused by commonly used stringent conditions, for example, during hydrodesulfurization, during the removal of thiophene compounds (such as, for example, thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes, etc.), which are some of the sulfur compounds that are most difficult to remove from cracked gasoline. In addition, it is necessary to avoid the use of systems in which conditions lead to a decrease in the content of aromatic compounds in cracked gasoline due to saturation. Accordingly, there is a need for a process that provides desulfurization and supports an octane rating.

In addition to the need to remove sulfur from cracked gasolines in the petroleum industry, there is a need to reduce the sulfur content of diesel fuel. In the general case, it is much more difficult to remove sulfur from diesel fuel than from gasoline. When sulfur is removed from diesel fuel by hydrodesulfurization, its cetane number improves, but the cost of the hydrogen used is high. Hydrogen is used in this case both for hydrodesulfurization and for the hydrogenation of aromatic compounds.

Accordingly, there is a need for a desulfurization process without significant hydrogen consumption in order to provide a more economical process for processing cracked gasolines and diesel fuel.

Due to the lack of success in providing an efficient and economically feasible process for reducing the sulfur content of cracked gasolines and diesel fuel, it is obvious that there is a need for an improved method for desulfurization of such hydrocarbon streams that would have a minimal effect on the octane number while providing a significant reduction in sulfur content.

Traditionally, compositions used in processes for removing sulfur from hydrocarbon streams are agglomerates used for fixed bed applications. Due to the various advantages of carrying out the process in a fluidized bed, hydrocarbon streams are sometimes processed in fluidized bed reactors. Fluidized bed reactors have advantages over fixed bed reactors, such as, for example, better heat transfer and better pressure drop. In fluidized bed reactors, particulate reagents are usually used. The size of such particles is usually in the range from about 1 micron to about 1000 microns. However, such commonly used reagents do not have sufficient abrasion resistance for all applications. Therefore, it is desirable to create a composition with a sufficiently high abrasion resistance, which removes sulfur from these hydrocarbon streams and can be used in fluidized-bed reactors, transport reactors, mobile reactors or fixed-bed reactors, and the development of a method for producing such a composition in an economical way, which was would be a significant contribution to this technical field and to the economy.

It is desirable to develop new methods for producing such compositions that can be used to desulfurize hydrocarbon streams.

In addition, it is desirable to create a method for removing sulfur from hydrocarbon streams, which would minimize the consumption of hydrogen and saturation of olefins and aromatic compounds contained in such streams.

It is also desirable to obtain an increased content of activator in the compositions, which helps to remove sulfur from diesel fuel.

In addition to the above, it is desirable to create a desulfurized cracked gasoline that contains less than about 100 ppm, preferably less than 50 ppm, of sulfur based on the weight of the desulfurized cracked gasoline and which contains substantially the same amount of olefins and aromatics as in the cracked gasoline from which such desulfurized cracked gasoline is made. It is also desirable to create a desulfurized diesel fuel.

The first embodiment of the present invention contains a new method for producing a composition, which includes:

a) mixing: 1) a liquid, 2) a compound containing zinc, 3) a material containing silicon dioxide, 4) aluminum oxide and 5) an activator to form a mixture of these components;

b) drying the resulting mixture to form a dried mixture;

c) calcining the dried mixture to form a calcined mixture;

d) recovering the calcined mixture with a suitable reducing agent under suitable conditions to obtain a composition containing a reduced valence activator, and

e) separating the resulting composition.

A second embodiment of the present invention includes another new method for preparing a composition, which comprises:

a) mixing: 1) a liquid, 2) a compound containing metal, 3) a material containing silicon dioxide, 4) alumina, and 5) a first activator to form a mixture of these components;

b) drying the resulting mixture to form a dried mixture;

c) combining the second activator with the dried mixture to form a combined mixture;

d) drying the combined mixture to form a dried combined mixture;

e) calcining the dried combined mixture to form a calcined activated mixture;

f) recovering the calcined activated mixture with a suitable reducing agent under suitable conditions to obtain a composition containing a reduced valence activator, and

g) separating the resulting composition.

A third embodiment of the present invention includes a method that includes, comprises, or substantially comprises:

(a) mixing: 1) a liquid, 2) a compound containing metal, 3) a material containing silicon dioxide, and 4) an activator to form a mixture of these components;

(b) adding alumina to the resulting mixture to form a mixture containing alumina;

(c) drying the resulting mixture containing alumina to form a dried mixture;

(d) calcining the dried mixture to form a calcined mixture;

(e) recovering the calcined mixture with a suitable reducing agent under suitable conditions to obtain a composition containing a reduced valence activator, and

(f) separating the resulting composition.

A fourth embodiment of the present invention includes a method that includes, comprises, or substantially comprises:

(a) mixing: 1) a liquid, 2) a first metal formate, 3) a material containing silicon dioxide, 4) alumina, and 5) a second metal formate to form a mixture of these components;

(b) drying the resulting mixture to form a dried mixture;

(c) calcining the dried mixture to form a calcined mixture; and

(d) reducing the calcined mixture with a reducing agent under appropriate conditions to obtain a composition containing a low valence activator, and

(e) separating the resulting composition.

A fifth embodiment of the present invention includes a method for removing sulfur from a hydrocarbon stream, comprising:

a) bringing the hydrocarbon stream into contact with the composition of the first or second, third or fourth embodiment in the desulfurization zone under conditions such as to produce a desulfurized hydrocarbon stream and a sulfurized composition;

b) separating the desulfurized hydrocarbon stream from the sulfurized composition and forming a separate stream of the desulfurized hydrocarbon stream and the separated sulfurized composition;

c) regenerating at least a portion of the separated sulfurized composition in the regeneration zone to remove at least a portion of the sulfur and / or sulfur contained therein and thereby form a regenerated composition;

d) recovering the regenerated composition in the reduction zone so as to form a reduced composition containing a low valence activator that will remove sulfur from the hydrocarbon stream when it is in contact with such a composition; and subsequent

e) returning at least a portion of the reconstituted composition to the desulfurization zone.

Other aspects, objects, and advantages of the invention will be apparent from the detailed description of the invention and the appended claims.

The term "gasoline" means a mixture of hydrocarbons boiling in the range from about 37.8 ° C to about 260 ° C, or any fraction of such a mixture. Examples of suitable gasoline include, but are not limited to, hydrocarbon streams in refineries such as naphtha, straight run naphtha, coking naphtha, catalytic cracking gasoline, visbreaking naphtha, alkylate, isomerate, reformate and the like. and their combinations.

The term “cracked gasoline” means a hydrocarbon mixture boiling in the range of from about 37.8 ° C. to about 260 ° C., or any fraction of such a mixture that is produced by a catalytic or thermal process that separates large hydrocarbon molecules into smaller molecules. Examples of suitable thermal processes include, but are not limited to, coking, thermal cracking, visbreaking, and the like. and their combinations. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil cracking, and the like. and their combinations. Accordingly, examples of suitable cracked gasoline include, but are not limited to, coking gasoline, thermal cracking gasoline, visbreaking gasoline, fluid catalytic cracking gasoline, heavy oil cracking gasoline, and the like. and their combinations. In some examples, such cracked gasoline may be fractionated and / or hydrogenated before desulfurization if used as a hydrocarbon stream in the process of this invention.

The term "diesel fuel" means a mixture of hydrocarbons boiling in the range from about 148.9 ° C to about 398.9 ° C, or any fraction of such a mixture. Examples of suitable diesel fuel include, but are not limited to, light recycle gas oil, kerosene, aviation fuel, straight run diesel fuel, hydrotreated diesel fuel, and the like. and their combinations.

The term "sulfur" means sulfur in any form, such as elemental sulfur or a sulfur compound, usually present in a fluid containing hydrocarbons, such as cracked gasoline or diesel fuel. Examples of sulfur that may be present in the process of this invention and typically contained in a hydrocarbon stream include, but are not limited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS 2 ), mercaptans (RSH), organic sulfides (RSR), organic sulfides (RSSR), thiophenes, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophenes, alkylthiophenes, alkydbenzothiophenes, alkyldibenzothiophenes and the like. and combinations thereof, as well as those compounds with a higher molecular weight, typically present in diesel fuel of those species contemplated for use in the process of this invention; in said compounds, R may be an alkyl, cycloalkyl or aryl group containing from one to ten carbon atoms.

The term “fluid” means gas, liquid, steam, and combinations thereof.

The term "gaseous" means that the state in which the fluid containing hydrocarbons, such as cracked gasoline or diesel fuel, is predominantly gaseous or vapor phase.

The term "abrasion resistance" means the abrasion resistance of a composition obtained by the method (s) of this invention. The term "Davison's Index" ("DI") means a measure of the stability of a composition to particle size reduction under controlled turbulent motion conditions. The higher the measured DI value, the lower the abrasion resistance of the composition.

The term "abrasion resistance improving component" means any component that can be added to a composition made by the methods of this invention to improve the abrasion resistance of such a composition compared to a composition that does not contain such an abrasion resistance improving component. Examples of a suitable component that improves abrasion resistance include, but are not limited to, clays, high alumina cements, romance, Portland cement, calcium aluminate, calcium silicate, talc and the like. and their combinations. The term "clay" means any clay that can be used as a component that improves the abrasion resistance of the composition of this invention. Examples of suitable clay include, but are not limited to, bentonite, sodium bentonite, acid washed bentonite, atapulgite, kaolin, kaolinite, montmorillonite, illite, halloysite, hectorite, sepiolite and the like. and their combinations. Preferably, such an abrasion resistance component comprises clay. More preferably, such an abrasion resistance improving component is selected from the group consisting of bentonite, sodium bentonite, acid washed bentonite, and the like. and their combinations. Most preferably, such an abrasion resistance improving component is bentonite.

The term "metal" means a metal in any form, such as an elemental metal or a compound containing a metal. A metal-containing compound that is a component separate from the activator in the composition (s) made by the methods of this invention may have a metal selected from the group consisting of zinc, manganese, silver, copper, cadmium, tin , lanthanum, scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum, gallium, indium, and combinations of any two or more of these metals. In the method used in the first embodiment, a zinc-containing compound is preferably used in the manufacture of a composition comprising zinc oxide.

The term "metal formate", as used here, means a compound formed by at least one metal ion and at least one formic acid ion. The formic acid ion is a carbon atom that is connected to a hydrogen atom and two oxygen atoms, while one of the oxygen atoms has a double bond with a carbon atom.

The term "metal oxide", as used here, means any metal oxide.

The term "metal oxide" also means a metal oxide in any form, such as a metal oxide or a metal oxide precursor.

Such metal oxide is preferably present in the composition manufactured by the method of this invention in an amount in the range of from about 10 to about 90 percent of the metal oxide content based on the total weight of the composition of this invention, more preferably in an amount in the range of from about 30 to about 80 percent metal oxide, and most preferably in an amount ranging from about 40 to about 70 percent metal oxide.

The term “activator” means any component that, when added to the composition of this invention, promotes desulfurization of hydrocarbon streams. Such activators may be at least one metal, metal oxide, metal oxide precursor, solid solution of two or more metals, or an alloy of two or more metals, in which the metal component is selected from the group consisting of nickel, cobalt, iron, manganese, copper , zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium and a combination of any two or more of these metals. In a fourth embodiment, such an activator is added to the composition as a second metal formate.

Some examples of compounds containing an activating metal include metal acetates, metal carbonates, metal nitrates, metal sulfates, metal thiocyanates, and the like. and their combinations. Preferably, the metal of such an activator is nickel.

A composition containing a low valence activator is a composition that has the ability to chemically and / or physically interact with sulfur. It is also preferred that such a composition remove diolefins and other gumming compounds from cracked gasoline.

During the preparation of the composition of this invention, an activator selected from the group consisting of metals, metal oxides, and the like. and combinations thereof, may initially be in the form of a compound containing a metal and / or a metal oxide precursor. It should be borne in mind that in the case where the activator is initially a compound containing a metal and / or a metal oxide precursor, part or all of such a compound and / or precursor may be converted to the corresponding metal or metal oxide during the time disclosed herein process according to this invention.

Typically, the activator in the normal oxidation state is in combination with a portion of the metal oxide of the composition of this invention made by the methods of the invention. The number of oxygen atoms bound to the activator must be reduced to form an activator with a reduced valency. Therefore, at least a portion of the activator present in the composition of this invention must be in the form of an activator with reduced valency. Without intentions to establish a connection with the theory, one can apparently assume that such an activator with reduced valency has the ability to chemisorb, separate, or remove sulfur. Accordingly, either the number of oxygen atoms bound to the activator must be reduced, or the oxidation state of the activator corresponds to a metal with zero valency. For example, if the activator metal is nickel, nickel oxide (NiO) can be used, and the low valence nickel (activator metal) can be either metallic nickel (Ni 0 ) or non-stoichiometric nickel oxide of the formula NiO (1-x) , where 0 <x <1. If tungsten is used as the activator metal, then tungsten oxide (WO 3 ) can be used, and tungsten with reduced valence (activator metal) can be tungsten oxide (WO 3 ), metal tungsten (W 0 ) or non-stoichiometric tungsten oxide of the formula WO ( 3-y) , where 0 <y <3.

Preferably, the activator is present in an amount that effectively removes sulfur from the hydrocarbon stream when it is in contact with the composition under desulfurization conditions. Preferably, of the total amount of activator present in the composition of this invention, at least 10 percent by weight of the activator is present as an activator with reduced valency, more preferably at least 40 percent of the activator is an activator with reduced valency, and most preferably so that at least 80 percent of the activator is a low valence activator for better sulfur removal activity. Such a reduced valency activator is typically present in a composition of this invention in an amount in the range of from about 1 to about 60 percent of the total weight of the composition of this invention, preferably in an amount in the range of from about 5 to about 40 percent, and most preferably in an amount ranging from 8 to 20 percent, for better sulfur removal activity. If the activator is a bimetallic activator, then in such an activator the ratio of the two metals forming it should be in the range from about 20: 1 to about 1:20.

The material containing silicon dioxide used in the manufacture of the compositions of this invention and present in them may be in the form of silicon dioxide or in the form of one or more materials containing silicon dioxide.

Any suitable material containing silica may be used in such a composition, such as, for example, diatomite, expanded perlite, colloidal silica, silica gel, precipitated silica, and the like. and their combinations. In addition, silicon compounds converted to silicon dioxide, such as silicic acid, ammonium silicate and the like, can also be used. and their combinations.

It is more preferable to use crushed expanded perlite as the material containing silicon dioxide. The term “perlite”, as used here, is a petrographic term for a siliceous volcanic rock that occurs naturally in certain regions of the world. A characteristic feature that distinguishes this rock from other volcanic minerals is its ability to expand from four to twenty times compared with the original volume when heated to a certain temperature. When heated above 871.1 ° C, crushed perlite expands due to the presence of bound water in the original pearlite rock. Bound water evaporates during heating and creates a lot of very small bubbles in the vitreous particles, softened by heat. These sealed bubbles in the vitreous material determine its low specific gravity. Expanded perlite can be ground to obtain a powder with increased porosity and low specific gravity of 2.5 pounds per cubic foot.

A typical elemental analysis of expanded perlite is as follows: 33.8% silicon, 7% aluminum, 3.5% potassium, 3.4% sodium, 0.6% calcium, 0.2% magnesium, 0.6% iron, 0.2 % impurity elements, 47.5% oxygen (by difference) and 3% bound water.

Typical physical properties of expanded perlite are as follows: a softening temperature of 1600-2000 ° F, a melting point of 2300-2450 ° F, a pH of 6.6-6.8, and a density of 2.2-2.4.

The term “ground expanded perlite” or “ground expanded perlite”, as used here, means a type of expanded perlite that was first milled to form particles from about 20 microns to about 500 microns in size, then heat treated with a fire heater at a temperature of about 871 , 1 ° C and finally crushed in a hammer mill.

Without intentions to establish a connection with any particular theory, it can apparently be assumed that the particle shape of the crushed expanded perlite affects the activity of the final composition made by the methods proposed in this invention.

Compositions obtained by the methods proposed in this invention contain a material containing aluminum selected from the group consisting of alumina, aluminate, and combinations thereof. To obtain these compositions can be used alumina. As such alumina used in the manufacture of the compositions, any suitable commercially available material containing aluminum may be used, at least a portion of which may be converted by calcination to aluminate. Examples include, but are not limited to, aluminum chlorides, aluminum nitrates, colloidal alumina solutions, hydrated alumina, peptized alumina, and typically those alumina compounds that are obtained by dehydration of alumina hydrates. A preferred alumina is hydrated alumina, such as, for example, boehmite or pseudoboehmite, for better activity and better sulfur removal. When the composition is exposed to high temperatures (for example, during calcination), at least a portion, preferably a large portion, of the alumina can be converted to aluminate, preferably alumina-zinc spinel.

The material containing aluminum is preferably present in the composition obtained by the methods of this invention in an amount in the range of from about 1.0 to about 30 percent, preferably in an amount in the range of from about 5 to about 25 percent, and most preferably in the range of 10 to 22 percent, based on the total weight of the composition.

The silica-containing material is preferably present in the composition obtained by the methods of this invention in an amount in the range of from about 10 to about 40 percent of the silica-containing material of the total composition, more preferably in an amount of from about 12 up to about 35 percent, and most preferably in the range of 15 to 30 percent. The composition may be particles in the form of granules, extrudates, tablets, pellets, pellets or microspheres. Preferably, the particles are microspheres capable of forming a fluidized bed.

In accordance with the first embodiment of the present invention, the composition can be obtained by the following method proposed in this invention.

a) mixing: 1) a liquid, 2) a compound containing zinc, 3) a material containing silicon dioxide, 4) aluminum oxide and 5) an activator to form a mixture of these components;

b) drying the resulting mixture to form a dried mixture;

c) calcining the dried mixture to form a calcined mixture;

d) recovering the calcined mixture with a suitable reducing agent under suitable conditions to obtain a composition containing a reduced valence activator, and

e) separating the resulting composition.

In the proposed production method according to the first embodiment, the composition can usually be obtained by mixing a liquid, a zinc-containing compound, a silica-containing material, aluminum oxide and an activator in an appropriate proportion by any suitable method or method that ensures uniform mixing of such components with the formation almost homogeneous mixtures thereof, including a liquid, a compound containing zinc, a material containing silicon dioxide, aluminum oxide and an asset torus. Optionally, an abrasion resistance component can also be added to such a mixture. The term "mixing", as used here, means mixing the components in any order and / or any combination or subcombination. However, in such an embodiment in which a liquid is mixed, a compound containing metal, a material containing silicon dioxide and an activator, alumina is added to the mixture after all other components. Any suitable means for mixing these components of the composition can be used to achieve the desired dispersion of these components. Examples of suitable mixers include, but are not limited to, mixing drums, mixers with fixed shelves or trays, Eurostar mixers, which can be batch or continuous type, percussion mixers, and the like. For this case, it is preferable to use Eurostar mixers when mixing the components of the composition according to this invention.

The liquid may be any solvent capable of dispersing a compound containing a metal, a material containing silicon dioxide, alumina and an activator; preferably, such a liquid may be selected from the group consisting of water, ethanol, acetone, and any combination thereof. The most preferred such liquid is water.

A metal-containing compound (preferably a zinc-containing compound) used in the manufacture of the composition in the first, second and third embodiments of the present invention may be in the form of metal oxide or in the form of one or more metal compounds that can be converted to metal oxide in the cooking conditions described here. Examples of suitable metal compounds include, but are not limited to, metal sulfide, metal sulfate, metal hydroxide, metal nitrate, metal formate, and the like. and their combinations. Preferably, such a metal-containing compound is in the form of a powdered metal oxide.

In the manufacture of particles from the resulting mixture, preferably by spray drying, a dispersant may optionally be added, and any suitable compound that facilitates spray drying of the mixture, preferably used as a suspension, may be added. In particular, these components may be useful in preventing sedimentation, precipitation, delamination, agglomeration, adhesion and sintering of solid particles in a fluid. Suitable dispersants include, but are not limited to, condensed phosphates, sulfonated polymers, and combinations thereof. The term "condensed phosphates" refers to any dehydrated phosphate containing more than one phosphorus atom and having a phosphorus-oxygen-phosphorus bond. Particular examples of suitable dispersants include sodium pyrophosphate, sodium metaphosphate, a sulfonated copolymer of styrene and maleic anhydride, and combinations thereof. The amount of dispersant used is typically in the range of from about 0.01 percent of the total weight of the components to about 10 percent. Preferably, the amount of dispersant used is typically in the range of from about 0.1 percent to about 8 percent.

In preparing a composition dried by a preferred spray drying, an acid component may be used. Typically, the acid in such an acidic component may be an organic acid or an inorganic acid such as nitric acid. If the acid component is an organic acid, it is preferable to use a carboxylic acid. If the acid component is an inorganic acid, it is preferable to use nitric acid or phosphoric acid. Mixtures of these acids may also be used. Typically, the acid is used with water to form a dilute aqueous acid solution. The amount of acid in the acidic component is usually in the range of from about 0.01 volume percent, based on the total volume of the acid component, to about 20 volume percent.

Typically, the spray dried material has an average particle size in the range of from about 10 micrometers to about 1000 micrometers, preferably in the range of from about 20 micrometers to about 150 micrometers.

The term "average particle size" refers to particle size of the material in its definition using RO-TAP ® Testing Sieve Shaker production WS Tyler Inc., Mentor, Ohio, or other comparable sieves. Material for measurements is placed in the upper part of the case of a standard group of sieves with a diameter of 8 inches with a stainless steel frame having a pallet in the bottom. The material is sieved for about 10 minutes, after which part of the material remaining on each of the sieves is weighed. The percentage of residue on each sieve is calculated by dividing the mass of material remaining on the corresponding sieve by the total weight of the original material sample. This information is used to calculate the average particle size.

The mixture is then dried to obtain a dried mixture. Drying conditions, as discussed herein, may include a temperature in the range of from about 65.5 ° C to about 550 ° C, preferably in the range of from about 87.8 ° C to about 210 ° C, and most preferably in the range of 93 , 3 ° C to 176.7 ° C. The conditions for such drying may also include a period of time, usually in the range of from about 0.5 hours to about 60 hours, preferably in the range of from about 1 hour to about 40 hours, and most preferably in the range of from 1.5 hours to 20 hours. Conditions for such drying may also include pressure, typically in the range of from about atmospheric pressure (i.e., about 14.7 psi of absolute pressure) to about 150 psi of absolute pressure, preferably in the range of about atmospheric pressure up to about 100 psi absolute pressure and most preferably near atmospheric pressure acting for a period of time at which the desired temperature can be maintained. Any drying methods known to those skilled in the art can be used, such as, for example, air drying, thermal drying, and the like. and their combinations. Thermal drying is preferably used.

The dried mixture is then calcined to form a calcined mixture. Preferably, the dried mixture is calcined in an oxidizing atmosphere, for example in the presence of oxygen or air. Calcination conditions, as discussed herein, may include a temperature in the range of from about 204.4 ° C to about 815.5 ° C, preferably in the range of from about 426.7 ° C to about 815.5 ° C, and more preferably in the range from 482.2 ° C to 760 ° C. The conditions for such calcination may also include pressure, typically in the range of from about 7 psig absolute pressure to about 750 psi absolute pressure, preferably in the range of about 7 psi absolute pressure to about 450 psi inch absolute pressure, and most preferably in the range from 7 psig absolute pressure to 150 psi absolute pressure, as well as a period of time in the range from about 1 hour to about 60 hours, preferably in the range of from about 1 hour to about 20 hours, and most preferably in the range of from 1 hour to 15 hours. In the method of this invention, such calcination can convert at least a portion of the alumina to aluminate.

The calcined mixture is then subjected to reduction with a suitable reducing agent, preferably hydrogen, so as to obtain a composition containing an activator with a generally low valency, preferably an activator with an essentially zero valency activator, when such an activator with zero valency is present in an amount that allows removal of sulfur from the stream hydrocarbons, such as cracked gasoline or diesel fuel, in accordance with the method disclosed in this invention.

Recovery conditions may include a temperature in the range of from about 37.8 ° C to about 815.5 ° C, a pressure in the range of from about 15 psig to about 1500 psig, and a sufficient amount of time for the formation of an activator with low valency.

The composition is then separated.

In accordance with a second embodiment of the present invention, the composition can also be obtained by the following method proposed in this invention:

a) mixing: 1) a liquid, 2) a compound containing metal, 3) a material containing silicon dioxide, 4) alumina, and 5) a first activator to form a mixture of these components;

b) drying the resulting mixture to form a dried mixture;

c) combining the second activator with the dried mixture to form a combined mixture;

d) drying the combined mixture to form a dried mixture;

e) calcining the dried combined mixture to form a calcined activated mixture;

f) recovering the calcined activated mixture with a suitable reducing agent under suitable conditions to obtain a composition containing a reduced valence activator, and

g) use of the resulting composition.

In this preparation of the composition of this invention, it can usually be obtained by mixing a liquid, a compound containing metal, a material containing silicon dioxide, alumina and a first activator in an appropriate proportion by any suitable method or method that ensures uniform mixing of such components with the formation of almost homogeneous mixtures thereof, including a liquid (as described above), a compound containing metal, a material containing silicon dioxide, alumina and an activator. Any suitable means for mixing these components, as described above, can be used to achieve the desired dispersion of these components.

The metal in the metal-containing compound is selected from the group consisting of zinc, manganese, silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum, gallium, indium, and combinations of any two or more than these metals. Preferably, the metal is zinc.

The metal-containing compound used in preparing the composition by the method of the present invention may be in the form of a metal oxide or in the form of one or more metal compounds that can be converted to a metal oxide under the manufacturing conditions described herein. Examples of suitable metal-containing compounds include, but are not limited to, metal sulfide, metal sulfate, metal hydroxide, metal carbonate, metal acetate, metal nitrate and the like. and their combinations. Preferably, such a metal-containing compound is in the form of a powdered metal oxide.

These components are mixed to form a mixture, which may be in the form selected from the group consisting of a wet mixture, a mixture in the form of dough, paste, suspension, and the like. Preferably, the mixture is in suspension. Such a mixture may optionally be formed by densification, extrusion, spray drying to form particles selected from the group consisting of granules, extrudates, tablets, pellets, pellets or microspheres, as described above.

The mixture is then dried to form a dried mixture in accordance with the drying conditions described above.

The dried mixture comprising a compound containing metal, a material containing silicon dioxide, and alumina (or aluminate) are then combined with a second activator. Optionally, the dried mixture may be calcined before combining with the second activator in accordance with the calcination conditions described above.

The terms “first activator” and “second activator” are used to distinguish between activators that are added to the mixture at different times. Both activators may contain the same element (i.e., nickel) or each of them may contain different elements (i.e., the first activator may contain nickel and the second activator may contain cobalt). The first activator and the second activator together comprise an activating component present in the separated composition of the second embodiment.

The second activator may be combined with the dried mixture by any suitable means or method known in the art for combining the activator with a base material.

A preferred method of combining is impregnation using any conventional wet impregnation technique (i.e., substantially completely or partially filling the pores of the base material with a solution of the combined elements) to impregnate the base. This preferred method uses an impregnation solution containing the desired activator concentration to form an ultimately combined mixture, which can then be dried and calcined (which can convert at least a portion of the alumina to aluminate), followed by reduction with a reducing agent such as hydrogen.

A preferred impregnation solution is formed by dissolving a metal-containing compound in a solvent such as water, alcohols, esters, ethers, ketones and combinations thereof, with metal being preferred, metal salts such as metal chloride, nitrate as such compound metal, metal sulfate, and the like. and their combinations. Preferably, the mass ratio of the metal activator and the solvent in such a solution may be in the range of from about 1: 1 to about 4: 1, but more preferably if it is in the range of from 1.5: 1 to 3: 1. For a particulate material, it is preferable to impregnate with a nickel component using a solution containing nickel nitrate hexahydrate dissolved in water.

After combining, preferably by impregnating, the dried mixture with the second activator, the resulting combined mixture is dried under the conditions described above to form a dried combined mixture and calcined under the conditions described above to form a calcined combined mixture. The calcined combined mixture may then be subjected to reduction with a reducing agent, as described above, to obtain the desired composition. The composition may then be separated.

A third embodiment of the present invention is a method that comprises, comprises, or substantially comprises:

(a) mixing: 1) a liquid, 2) a compound containing metal, 3) a material containing silicon dioxide, and 4) an activator to form a mixture of these components;

(b) adding alumina to the resulting mixture to form a mixture containing alumina;

(c) drying the resulting mixture containing alumina to form a dried mixture;

(d) calcining the dried mixture to form a calcined mixture;

(e) recovering the calcined mixture with a suitable reducing agent under suitable conditions to obtain a composition containing a reduced valence activator, and

(f) separating the resulting composition.

In preparing the composition of the third embodiment, it can usually be obtained by mixing a liquid, a compound containing a metal, materials containing silicon dioxide, and an activator. These components can, as a rule, be mixed in the same manner as described above. The metal-containing compound used is the same as that described for the second embodiment above.

Such a mixture may be in the form selected from the group comprising a wet mixture, a mixture in the form of dough, paste, suspension, and the like.

After mixing the components mentioned above, alumina can then be added to the resulting mixture to form a mixture containing alumina.

The resulting alumina-containing mixture is then dried and calcined as described above.

In accordance with a fourth embodiment of the present invention, the composition can also be obtained by the following method proposed in this invention:

(a) mixing: 1) a liquid, 2) a first metal formate, 3) a material containing silicon dioxide, 4) alumina, and 5) a second metal formate to form a mixture of these components;

(b) drying the resulting mixture to form a dried mixture;

(c) calcining the dried mixture to form a calcined mixture; and

(d) separating the resulting composition.

The composition can usually be obtained by mixing (in the same manner as described above) a liquid, a first metal formate, a material containing silicon dioxide, alumina, and a second metal formate to form a mixture of these components.

The metals in the first and second metal formates may be different, or they may be the same metal. Preferably, the first metal formate is zinc formate and the second metal formate is nickel formate.

In a fourth embodiment, the activator is in the form of a metal formate. Also in the fourth embodiment, the above components of the composition are mixed to form a mixture, which may be in the form selected from the group consisting of a wet mixture, a mixture in the form of dough, paste, suspension, and the like. Preferably, the mixture is in suspension. Such a mixture may be formed to form particles selected from the group consisting of granules, extrudates, tablets, balls, pellets or microspheres.

Preferably, said liquid is ammonium hydroxide or ammonia.

After mixing, the resulting mixture is dried and calcined as described above.

A fifth embodiment of the present invention includes a new method for removing sulfur from a hydrocarbon stream. This method includes:

a) bringing the hydrocarbon stream into contact with the composition of the first or second embodiment of the present invention in a desulfurization zone under conditions such that a desulfurized hydrocarbon stream and a sulfurized composition are formed;

b) separating the desulfurized hydrocarbon stream from the sulfurized composition and forming a separate stream of the desulfurized hydrocarbon stream and the separated sulfurized composition;

c) regenerating at least a portion of the separated sulfurized composition in the regeneration zone in order to remove at least a portion of the sulfur contained therein and / or on it and thereby form a regenerated composition;

d) recovering the regenerated composition in the reduction zone so as to form a reduced composition containing a reduced valency activator that can remove sulfur from the hydrocarbon stream when it is in contact with such a composition; and subsequent

e) returning at least a portion of the reconstituted composition to the desulfurization zone.

Bringing the hydrocarbon stream into contact with step a) with a composition made by the methods of the first or second embodiment in the desulfurization zone can be performed by any method known to those skilled in the art.

The desulfurization zone may be any zone in which desulfurization of a hydrocarbon stream may take place. Examples of suitable zones are fixed bed reactors, moving bed reactors, fluidized bed reactors, transport reactors, and the like. For this case, it is preferable to use a fluidized bed reactor or a fixed bed reactor.

The desulfurization zone in step a) has the following conditions: total pressure, temperature, hourly average feed rate and hydrogen consumption. These conditions are such that the composition of the invention can desulfurize a hydrocarbon stream to form a desulfurized hydrocarbon stream and a sulfurized composition.

The total pressure may range from about 15 psi absolute pressure to about 1,500 psi absolute pressure. However, for this case, it is preferable that the total pressure is in the range of from about 50 psig absolute pressure to about 500 psig absolute pressure.

In general, the temperature should be sufficient to maintain the flow of hydrocarbons mainly in the form of a vapor or gas phase. While this temperature may be in the range of from about 37.8 ° C to about 537.8 ° C, for this case, it is preferable that the temperature is in the range of from about 204.4 ° C to about 426.7 ° C when processing cracked gasoline and in the range from about 260 ° C to about 482.2 ° C when processing diesel fuel.

The hourly average feed rate (“WHSV”) is defined as the numerical ratio of the flow rate with which the hydrocarbon stream enters the desulfurization zone, in pounds per hour under normal conditions of temperature and pressure (STP) and the mass in pounds of the composition in the desulfurization zone, in which receives the specified stream of hydrocarbons. When applying the present invention, the WHSV value should be in the range of from about 0.5 h −1 to about 50 h −1 , preferably in the range of from about 1 h −1 to about 50 h −1 .

Any suitable hydrocarbon stream that contains sulfur-containing hydrocarbons or consists entirely or mainly of such hydrocarbons can be used as a feed material brought into contact with the composition of this invention. The hydrocarbon stream preferably contains a fuel selected from the group consisting of cracked gasoline, diesel fuel, and combinations thereof, or consists entirely or mainly of such fuel.

The amount of sulfur in such a hydrocarbon stream may range from less than 10 ppm sulfur based on the weight of the hydrocarbon stream to about 50,000 ppm. If the hydrocarbon stream is cracked gasoline, then the amount of sulfur may be in the range from less than 10 ppm sulfur based on the weight of cracked gasoline to about 10,000 ppm sulfur based on the weight of cracked gasoline. If the hydrocarbon stream is diesel fuel, then the amount of sulfur may be in the range of from less than about 10 ppm sulfur based on the weight of diesel fuel to about 50,000 ppm sulfur based on the weight of diesel fuel.

The terms “sulfur” or “ppm sulfur by weight” as used herein mean the amount of elemental sulfur (approximately 32 atomic units of mass) contained in the sulfur-containing hydrocarbons of a hydrocarbon stream, based on the total weight of the hydrocarbon stream, and not atomic mass or a mass of a sulfur compound, such as an organic sulfur compound.

Cracked gasoline or diesel fuel suitable as a feed material in the method of this invention is a composition that contains, in particular, olefins, aromatics, sulfur, paraffins and naphthenes.

The amount of olefins in cracked gasoline is typically in the range of from about 10 to about 35 percent olefins based on the total weight of the cracked gasoline. In diesel fuel, olefins are generally absent.

The amount of aromatic compounds in cracked gasoline is usually in the range of from about 20 to about 40 percent aromatic compounds based on the total weight of the cracked gasoline. The amount of aromatic compounds in diesel fuel is typically in the range of from about 10 to about 90 percent aromatic compounds based on the total weight of diesel fuel.

When performing the desulfurization step of the process of this invention, it is preferred that the hydrocarbon stream is in the form of a gas or vapor phase. However, when applying the present invention, it is not essential that such a hydrocarbon stream is completely in the form of a gas or vapor phase.

When performing the desulfurization step in this case, it is preferable that an agent be used that interferes with any chemical or physical interaction of the olefinic or aromatic compounds in the hydrocarbon stream processed using the composition of the invention. Preferably, such an agent is hydrogen.

The hydrogen stream in the desulfurization zone is usually such that the molar ratio of hydrogen to hydrocarbon stream is in the range of from about 0.1 to about 10, preferably in the range of from about 0.2 to about 3.

If desired, diluents such as methane, carbon dioxide, flue gas, nitrogen and the like can be used during desulfurization of cracked gasoline or diesel fuel. and their combinations. Accordingly, when applying the present invention, it is not essential that pure hydrogen be used to achieve the desired desulfurization of a hydrocarbon stream such as cracked gasoline or diesel fuel, but not limited to them.

In this case, when using a system with a fluidized bed reactor, it is preferable that the composition used have a particle size in the range of from about 10 micrometers to about 1000 micrometers. Preferably, such a composition should have a particle size in the range of from about 20 micrometers to about 500 micrometers, and more preferably in the range of 30 micrometers to 400 micrometers. When using a fixed-bed reactor system to practice the desulfurization method of the present invention, the composition will typically have a particle size in the range of about 1/32 inch to about 1/2 inch in diameter, preferably in the range of about 1/32 inch to approximately 1/4 inch in diameter.

In addition, for this case, it is preferable to use a composition with a specific surface area in the range from about 1 square meter per gram (m 2 / g) to about 1000 square meters per gram of the composition, preferably in the range from about 1 m 2 / g to about 800 m 2 / g.

The desulfurized hydrocarbon stream may be separated from the sulfurized composition by any suitable separation method known in the art to form a separated stream of a desulfurized hydrocarbon stream and a separated sulfurized composition.

Examples of such agents are cyclones, settling chambers, percussion devices for separating solid particles and gases, and the like. and their combinations. The separation may include, but without limitation, ensuring the flow of hydrocarbons from the desulfurization zone. The desulfurized cracked gas gas or the desulfurized gaseous diesel fuel may then be separated and preferably liquefied. The liquefaction of such desulfurized hydrocarbon streams may be performed in any manner known in the art.

The amount of sulfur in such a desulfurized hydrocarbon stream obtained by treatment in accordance with the desulfurization method of the invention is less than about 500 ppm sulfur based on the weight of the hydrocarbon stream, preferably less than about 150 ppm sulfur based on the weight a hydrocarbon stream, and more preferably less than about 50 ppm sulfur, based on the weight of the hydrocarbon stream.

When performing the process by the method proposed in this invention, if desired, a stripper can be installed before and / or after regeneration of the sulfurized composition. Such a stripper may serve to remove a portion, preferably a total amount, of hydrocarbons from a sulfurized composition. Such a stripper may also serve to remove oxygen and sulfur dioxide from the system before introducing the regenerated composition into the reduction zone. Desorption contains a number of conditions, which include the total pressure, temperature, and partial pressure of the desorbing agent.

Preferably, the total pressure in the stripper, when used, ranges from about 25 psi absolute pressure to about 500 psi absolute pressure.

The temperature for such desorption may range from about 37.8 ° C to about 537.8 ° C.

A desorbing agent is a composition that promotes the removal of hydrocarbons from a sulfurized composition. Preferably, such a stripping agent is nitrogen. Sulfurized composition may contain sulfur inside itself (for example, in the pores of the composition) or on top of itself (for example, placed on the surface of the composition).

The regeneration zone uses a number of conditions, which include the total pressure and the partial pressure of the agent to remove sulfur. The total pressure typically ranges from about 25 psi absolute pressure to about 50 psi absolute pressure.

The partial pressure of the sulfur removal agent is usually in the range of from about 1% to about 25% of the total pressure.

Such a sulfur removal agent is a composition that promotes the formation of gaseous sulfur-containing compounds and oxygen-containing compounds such as sulfur dioxide, as well as the combustion of any residual hydrocarbons that may be present. A preferred sulfur removal agent suitable for use in the regeneration zone is an agent selected from the group including, but not limited to, gases containing oxygen, such as air.

The temperature in the regeneration zone is usually in the range of from about 37.8 ° C to about 815.5 ° C, preferably in the range of from about 426.7 ° C to about 648.9 ° C.

As the regeneration zone, any reservoir may be used in which desulfurization or regeneration of the sulfurized composition may occur.

The regenerated composition is then reduced in the reduction zone with a reducing agent including hydrogen, but not limited thereto, so that at least a portion of the activator contained in such a composition is reduced to form a reduced composition containing a reduced valence activator that can remove sulfur from a hydrocarbon stream in accordance with the method disclosed herein.

In the General case, in the practical use of the present invention, the restoration of the desulfurized composition is performed at a temperature in the range from about 37.8 ° C to about 815.5 ° C and at a pressure in the range from about 15 psig absolute pressure to about 1500 psi inch of absolute pressure. Such recovery is carried out for a time sufficient to achieve the desired level of recovery of the activator, which is preferably contained in the surface layer of the composition. Such recovery can usually be achieved over a period of time ranging from about 0.01 hours to about 20 hours.

After reconstituting the regenerated composition, at least a portion of the resulting reconstituted composition may be returned to the desulfurization zone.

When carrying out the process by the method proposed in this invention, the stage of desulfurization, regeneration, recovery and, optionally, desorption before and / or after such regeneration can be performed in one zone or reservoir or in several zones or reservoirs.

When carrying out the process by the method proposed in this invention, in a system with a fixed-bed reactor, the stages of desulfurization, regeneration, recovery and, optionally, desorption before and / or after such regeneration are performed in one zone or tank.

Desulfurized cracked gasoline can be used in gasoline blends to provide gasoline products for commercial use and can also be used where low sulfur cracked gasoline is required.

Desulfurized diesel fuel can be used as part of diesel fuel mixtures to obtain diesel fuel brands.

Example I (according to this invention)

A composition of zinc oxide, alumina and perlite activated with nickel was prepared. 56 grams of Vista Dispal alumina was added to 118.43 grams of deionized water and mixed for 20 minutes. Then, 43.6 grams of the base (prepared by treating perlite with nitric acid followed by the addition of alumina, zinc oxide and kaolin) was added to the mixture of water and alumina over 5 minutes, followed by stirring for an additional five minutes. This mixture will be referred to in the following description as to Mixture No. 1.

In addition, 0.03 grams of nitric acid was added to 473.73 grams of deionized water and mixed for five minutes. Thereafter, 55.6 grams of perlite (Silbrico Sil-Kleer # 27-M) was added to the resulting nitric acid solution over five minutes and mixed for 20 minutes. Then, 198 grams of nickel nitrate was added to the perlite solution over 5 minutes and mixed for 15 minutes. This mixture will be referred to as Mixture No. 2 in the further description.

Mixture No. 2 was then poured into Mixture No. 1 and stirred for 10 minutes. Thereafter, 204.8 grams of zinc oxide was added to the resulting mixture over five minutes, and then stirred for an additional 15 minutes. The zinc oxide mixture was spray dried and then dried in an oven.

A mixture of zinc oxide in an amount of 100 grams was impregnated using an ultrasonic nozzle by a combination of 87.5 grams of nickel nitrate hexahydrate with 13.75 grams of deionized water. The impregnated mixture was dried at 150 ° C for 1 hour and calcined at 635 ° C for 1 hour. The value of the Davison index (DI) for this composition was 10.3.

Example II

The composition made in Example I was tested for its desulfurization activity as follows. 10 grams of the prepared material was placed in a quartz tube with a diameter of 1/2 inch and a length of about 12 inches, having a glassy frit located above the bottom one third to provide inert support for the composition layer.

During each reaction cycle, such a reactor was maintained at a temperature of 398.9 ° C. and a pressure of 15 psi absolute pressure. The flow of hydrogen was 130 standard cubic centimeters per minute and was diluted with nitrogen at a rate of 130 standard cubic centimeters per minute. The supplied diesel fuel used as a sample was pumped from above through the reactor at a flow rate of 13.4 ml per hour. Such conditions are hereinafter referred to as “reaction conditions”.

The supplied diesel fuel had a sulfur content of 135 ppm (ppm). This sulfur was in the form of 4,6-dimethyldibenzothiophene. This compound is the most difficult to remove sulfur-containing compound due to steric hindrances.

Before starting Cycle 1, this composition was restored with hydrogen flowing at a rate of 300 standard cubic centimeters per minute at a temperature of 398.9 ° C for one hour. Such conditions are hereinafter referred to as “recovery conditions”. Each reaction cycle was four hours when measuring the sulfur content (ppm) in the product after one, two, three and four hours of exposure to the feed product for each cycle.

After completion of the reaction cycle, the composition was washed with nitrogen at a rate of 180 standard cubic centimeters per minute at 398.9 ° C for fifteen minutes. The temperature was then raised to 537.8 ° C and the composition was regenerated at an air flow rate of 120 standard cubic centimeters per minute and a nitrogen flow rate of 180 standard cubic centimeters per minute for two hours. The temperature was then reduced to 398.9 ° C and the sample was purged with nitrogen for 15 minutes. Such conditions are hereinafter referred to as “regeneration conditions”. Cycle 2 began, like Cycle 1, under recovery conditions; those. processing the composition at 398.9 ° C with hydrogen at a flow rate of 300 standard cubic centimeters per minute for one hour.

The composition of Example I was tested for two reaction cycles during the regeneration carried out after Cycle 1. The results obtained are presented in table I, in which the given values indicate the sulfur content of the product in parts per million by weight after the first hour, second hour, third hour and fourth hours of processing, respectively.

Table I
Served Product: 135 ppm sulfur
Time Cycle 1 (ppm sulfur) Cycle 2 (ppm sulfur) First hour 65 47 Second hour 82 76 Third hour 86 90 Fourth hour 91 98

Example III (control)

70 grams of the base (prepared by treating perlite with nitric acid followed by the addition of alumina, zinc oxide and kaolin) was impregnated with nickel in two steps using a conventional wet impregnation technique. For each impregnation step, 74.3 grams of nickel nitrate hexahydrate in 7 grams of deionized water was used. After the first impregnation, the composition was dried at a temperature of 150 ° C for 1 hour. After the second impregnation, the composition was dried at 150 ° C for 1 hour and calcined at 635 ° C for 1 hour. The DI value for this composition was 12.2.

Example IV

10 grams of the composition prepared in Example III was tested for its activity against desulfurization, as described in Example II. The composition was tested for two reaction cycles, the results of which are shown in table II in parts per million by weight of sulfur content in the product after the first hour, second hour, third hour and fourth hour of treatment, respectively.

Table II
Served Product - 135 ppm Sulfur
Time Cycle 1 (ppm sulfur) Cycle 2 (ppm sulfur) First hour 80 72 Second hour 90 95 Third hour 91 101 Fourth hour 97 106

Example V (control)

85 grams of the base (as described in Examples I and III) was impregnated with nickel in one step using a conventional wet impregnation technique. For impregnation, 74.3 grams of nickel nitrate hexahydrate in 7 grams of deionized water was used. The composition was dried at 150 ° C for 1 hour and calcined at 635 ° C for 1 hour. The DI value for this composition was 14.7.

Example VI

10 grams of the composition prepared in Example V was tested for its desulfurization activity as described in Example II. The composition was tested for two reaction cycles, the results of which are shown in table III in parts per million by weight of sulfur content in the product after the first hour, second hour, third hour and fourth hour of treatment, respectively.

Table III
Served Product - 135 ppm Sulfur
Time Cycle 1 (ppm sulfur) Cycle 2 (ppm sulfur) First hour 67 63 Second hour 76 94 Third hour 81 105 Fourth hour 89 108

In accordance with the presented results, the composition obtained by the method according to this invention in Example I, removes sulfur as well, if not better, as the compositions prepared in Examples III and V.

Example VII

A composition of zinc oxide, alumina and perlite activated with nickel was prepared. 685 grams of distilled water were mixed with 1,007.5 grams of nickel nitrate hexahydrate. Then, 146 grams of Condea Disperal alumina was added to the mixture. In addition, 150 grams of perlite (Silbrico Sil-Kleer # 27-M) was mixed with 575 grams of zinc oxide. This mixture was then added to the alumina mixture. The composition was then dried and calcined, as disclosed in the previous examples.

Example VIII

30 grams of nickel diformate dihydrate was dissolved in 200 ml of concentrated ammonium hydroxide. Then, 45 grams of zinc diformate dihydrate was added to the resulting solution. After that, 20 grams of alumina was slowly added to the solution with stirring. This solution was heated on a heated plate of the mixer until ammonia was removed from it. Then 10 g of expanded expanded perlite was added. This composition was filtered and washed, after which it was dried at 110 ° C and restored at 300 ° C for 1 hour.

Example IX

The composition made in Example VIII was tested for its desulfurization activity as follows. 10 grams of the prepared material was placed in a quartz tube with a diameter of 1/2 inch and a length of about 12 inches, having a vitreous frit, located above the bottom one third to provide internal support for the composition layer.

The composition was restored at a temperature of 398 ° C with a stream of hydrogen with a flow rate of 300 cubic cm / min. These conditions are then referred to as “recovery conditions”.

During each reaction cycle, the reactor was maintained at a temperature of 398 ° C and a pressure of 15 psi absolute pressure. The flow rate of hydrogen was 80 cubic cm / min. The nitrogen flow rate was 120 cubic cm / min. The supplied diesel fuel used as a sample was pumped from above through the reactor at a flow rate of 72 cubic cm / min. Such conditions are hereinafter referred to as “reaction conditions”.

The supplied diesel fuel had a sulfur content of 135 ppm (ppm). Sulfur was in the form of 4,6-dimethyldibenzothiophene. This compound is the most difficult to remove sulfur-containing compound due to steric hindrances.

Each reaction cycle was 4 hours when measuring the sulfur content (ppm) in the product after 1, 2, 3, and 4 hours of exposure to the feed product for each cycle.

After the completion of the reaction cycle, the composition was washed with nitrogen at a rate of 180 cc / min at 398 ° C for 15 minutes. The temperature was then raised to 549 ° C and the composition was regenerated at an air flow rate of 50 cubic cm / min and a nitrogen flow rate of 180 cubic cm / min for 2 hours. The temperature was then reduced to 398 ° C and the sample was purged with nitrogen for 15 minutes. Such conditions are hereinafter referred to as “regeneration conditions”. Cycle 2 began, like Cycle 1, under recovery conditions; those. from treating the composition at 398 ° C with hydrogen at a flow rate of 300 cubic cm / min for 1 hour.

The composition of Example VIII was tested for 3 reaction cycles during regeneration carried out after cycles 1 and 2. The results are shown in Table IV, in which the given values indicate the sulfur content in the product in parts per million by weight after the 1st hour, 2nd hours, 3 hours and 4 hours of processing, respectively.

Table IV
Granular composition
Served Product - 135 ppm Sulfur
Time Cycle 2 (ppm sulfur) Cycle 3 (ppm sulfur) First hour 7 8 Second hour four 8 Third hour 8 17 Fourth hour 33 46

Example X

300 grams of nickel diformate dihydrate was dissolved in 2000 ml of a concentrated solution of ammonium hydroxide. Then, 45 grams of zinc diformate dihydrate was added to the resulting solution. After that, 200 grams of alumina was slowly added to the solution with stirring. This solution was heated on a heated plate of the mixer until no more ammonia remained in the solution. Then, 80 grams of expanded expanded perlite was added to the solution. The solution was then filtered and washed, and then spray dried. The resulting composition was restored at 360 ° C for 1 hour in a stream of hydrogen.

Example XI

10 grams of the composition prepared in Example X was tested for its desulfurization activity, as described in Example IX. The composition was tested for 3 reaction cycles, the results of which are shown in table V in parts per million by weight of sulfur content in the product after the 1st hour, 2nd hour, 3rd hour, and 4th hour of treatment, respectively.

Table v
Spray-dried Composition
Served Product - 135 ppm Sulfur
Time Cycle 2 (ppm sulfur) Cycle 3 (ppm sulfur) First hour 39 38 Second hour 24 34 Third hour 38 43 Fourth hour 54 63

Example XII

The suspension containing alumina, perlite, zinc oxide and water was spray dried to form microspheres. These microspheres were then impregnated with a nickel nitrate solution to obtain a nominal nickel content of 17 weight percent. The impregnated microspheres were dried at 150 ° C and calcined at 635 ° C.

Example XIII

10 grams of the composition prepared in Example XII was tested for its desulfurization activity as described in Example IX. The composition was tested for 3 reaction cycles, the results of which are shown in table VI in parts per million by weight of sulfur content in the product after the 1st hour, 2nd hour, 3rd hour, and 4th hour of treatment, respectively.

Table VI
Spray-dried Composition
Served Product - 135 ppm Sulfur
Time Cycle 2 (ppm sulfur) Cycle 3 (ppm sulfur) First hour 54 44 Second hour 65 71 Third hour 81 89 Fourth hour 88 99

Example XIV

0.025 grams of nitric acid was added to 440 ml of deionized water and stirred for 5 minutes. Then, 55.6 grams of perlite was added to the resulting nitric acid solution and mixed for 20 minutes. After that, 125 grams of nickel hydroxide was added to the resulting solution and stirred for 15 minutes. Then, 43.6 grams of kaolin was added to the solution and mixed for 5 minutes. After that, 204.8 grams of zinc oxide was added to the resulting solution over 5 minutes and stirred for 15 minutes. In a separate container, 56 grams of alumina was added to 118.43 ml of water over 5 minutes and mixed for 20 minutes. Then, the alumina solution was poured into a zinc / nickel solution and stirred for 15 minutes. The resulting suspension was then spray dried. The resulting composition was dried at 150 ° C for 1 hour and calcined at 635 ° C for 1 hour.

Example XV

10 grams of the composition prepared in Example XIV was tested for its desulfurization activity, as described in Example IX. The composition was tested for 3 reaction cycles; the results for the 2nd and 3rd cycles are shown in Table VII in parts per million by weight of sulfur content in the product after the 1st hour, 2nd hour, 3rd hour and 4th hour of treatment, respectively.

Table VII
Served Product - 135 ppm Sulfur
Time Cycle 2 (ppm sulfur) Cycle 3 (ppm sulfur) First hour 64 72 Second hour 68 84 Third hour 89 94 Fourth hour 94 108

Example XVI

0.026 grams of nitric acid was added to 413.05 ml of water and stirred for 5 minutes. Then, 74.01 grams of perlite was added to the resulting nitric acid solution over 5 minutes and mixed for 15 minutes. Then, 273.94 grams of zinc oxide was added to the perlite solution over 5 minutes and mixed for 15 minutes. Then, 74.49 grams of alumina was added to 137.68 ml of water over 5 minutes and mixed for 20 minutes. Then, 58.15 grams of kaolin were added to the alumina solution over 5 minutes and mixed for 5 minutes. After that, the perlite solution was poured over 5 minutes into the alumina solution while stirring the alumina solution. The resulting combined solution was stirred for 15 minutes and then spray dried. To this suspension was then added 25 grams of water. 113 grams of nickel nitrate hexahydrate was heated with 10 grams of deionized water to dissolve it. The solution was then combined with 120 grams of an alumina composition. The final composition was then dried at 150 ° C for 1 hour and calcined at 635 ° C for 1 hour.

Example XVII

10 grams of the composition prepared in Example XVI, was tested for its activity against desulfurization, as described in Example IX. The composition was tested for 3 reaction cycles, the results of which are shown in table VIII in parts per million by weight of sulfur content in the product after the 1st hour, 2nd hour, 3rd hour and 4th hour of treatment, respectively.

Table VIII
Served Product - 135 ppm Sulfur
Time Cycle 2 (ppm sulfur) Cycle 3 (ppm sulfur) First hour 61 74 Second hour 80 99 Third hour 94 108 Fourth hour 97 114

While the invention has been described above in detail for illustrative purposes, it should not be construed as being limited to this description, and it should be borne in mind that this invention covers all variations and modifications that are included within the spirit and scope of this invention.

Claims (26)

1. A method of obtaining a composition for removing sulfur from a stream of hydrocarbons, including:
(a) mixing: 1) a liquid, 2) a first metal formate, 3) a material containing silicon dioxide, 4) alumina, and 5) a second metal formate, to form a mixture of these components;
(b) drying said mixture to form a dried mixture;
(c) calcining said dried mixture to form a calcined mixture; and
(d) reducing the calcined mixture with a reducing agent under reducing conditions to obtain a composition containing a reduced valence activator,
(e) separating the resulting composition,
wherein said calcined reduced mixture helps to remove sulfur from the hydrocarbon stream by contacting the hydrocarbon stream under desulfurization conditions, and wherein said liquid is ammonia.
2. The method according to claim 1, in which the first metal formate contains a metal selected from the group consisting of zinc, manganese, copper, cadmium, tin, iron, gallium, and a combination of two or more of these metals.
3. The method according to claim 1, wherein said first metal formate is zinc formate.
4. The method according to claim 1, in which the second metal formate contains a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, tin, antimony, platinum, chromium, palladium and a combination of any two or more of these metals.
5. The method according to claim 1, wherein the second metal formate is nickel formate.
6. The method according to claim 1, wherein said material containing silicon dioxide is in the form of crushed expanded perlite.
7. The method according to claim 1, wherein said mixture from step (a) is in the form of a wet mixture, dough, paste or suspension.
8. The method according to claim 7, wherein said mixture from step (a) is in the form of a suspension.
9. The method according to claim 1, wherein said mixture from step (a) is ground before drying in step (b).
10. The method according to claim 1, in which the specified mixture from stage (a) is ground in the form of granules, extrudates, tablets, balls, pellets or microspheres.
11. The method according to claim 1, wherein said mixture from step (a) is ground by spray drying in step (b) to form said dried mixture.
12. The method according to claim 1, wherein said mixture is dried in step (b) at a temperature in the range of from about 65.5 ° C to about 550 ° C.
13. The method according to claim 1, wherein said dried mixture is calcined in step (c) at a temperature in the range of from about 204.4 ° C. to about 815.5 ° C.
14. The method according to claim 1, in which the recovery of the specified calcined mixture is performed in stage (d) at a temperature in the range from about 37.4 ° C to about 815.5 ° C and at a pressure in the range from about 15 to about 1,500 pounds per square inch of absolute pressure for a time sufficient to form an activator with reduced valency.
15. The method according to claim 1, wherein during said calcination in step (c), at least a portion of said alumina is converted to aluminate.
16. A composition for removing sulfur from hydrocarbon streams obtained by the method according to claim 1.
17. A method for removing sulfur from a hydrocarbon stream, comprising:
(a) contacting said hydrocarbon stream with a composition obtained by the method according to claim 1 in a desulfurization zone under conditions such that a desulfurized hydrocarbon stream and a sulfurized composition are formed;
(b) separating said desulfurized hydrocarbon stream from said sulfurized composition and forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition;
(c) regenerating at least a portion of said separated sulfonated composition in a regeneration zone in order to remove at least a portion of the sulfur and / or sulfur contained therein and thereby form a regenerated composition;
(d) recovering said regenerated composition in a reduction zone so as to form a reduced composition containing a reduced valence activator that can remove sulfur from the hydrocarbon stream when it is in contact with such a composition; and subsequent e) returning at least a portion of said reduced composition to said desulfurization zone.
18. The method of claim 17, wherein said hydrocarbon stream comprises fuel selected from the group consisting of cracked gasoline, diesel fuel, and a combination thereof.
19. The method of claim 17, wherein said desulfurization in step (a) is performed at a temperature in the range of from about 37.8 ° C to about 537.8 ° C and at a pressure in the range of from about 15 to about 1,500 psi inch absolute pressure for a time sufficient to remove sulfur from the specified stream.
20. The method of claim 17, wherein said regeneration in step (c) is performed at a temperature in the range of from about 37.8 ° C to about 815.5 ° C and at a pressure in the range of from about 10 to about 1,500 psi an inch of absolute pressure for a time sufficient to remove at least a portion of the sulfur from said separated sulfonated composition.
21. The method according to 17, in which at the stage (C) use air as a regenerating agent in the specified regeneration zone.
22. The method according to 17, in which the recovered composition from stage (c) is subjected to hydrogen reduction in stage (d) in the specified regeneration zone, which is maintained at a temperature in the range from about 37.8 ° C to about 815.5 ° C and at pressures in the range of about 15 to about 1,500 psi absolute pressure, for a period of time sufficient to reduce the valency of the activator contained in said regenerated composition.
23. The method according to 17, in which the specified sulfonated composition from stage (b) is subjected to desorption before introducing into the specified regeneration zone in stage (C).
24. The method according to 17, wherein said regenerated composition from step (c) is subjected to desorption before being introduced into said recovery zone in step (d).
25. Cracked gasoline obtained by the method according to p.
26. Diesel fuel obtained by the method according to p.
RU2007108545/04A 2003-07-23 2005-08-09 Desulphuration and novel desulphuration method RU2393919C2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/914,798 US20050020446A1 (en) 2003-07-23 2004-08-10 Desulfurization and novel process for same
US10/914,798 2004-08-10

Publications (2)

Publication Number Publication Date
RU2007108545A RU2007108545A (en) 2008-09-20
RU2393919C2 true RU2393919C2 (en) 2010-07-10

Family

ID=35908100

Family Applications (1)

Application Number Title Priority Date Filing Date
RU2007108545/04A RU2393919C2 (en) 2003-07-23 2005-08-09 Desulphuration and novel desulphuration method

Country Status (7)

Country Link
US (1) US20050020446A1 (en)
EP (1) EP1799794A4 (en)
JP (1) JP2008510035A (en)
CN (1) CN101432398B (en)
BR (1) BRPI0514299B1 (en)
RU (1) RU2393919C2 (en)
WO (1) WO2006020642A2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2559627C2 (en) * 2012-06-12 2015-08-10 Чайна Петролеум Энд Кемикал Корпорейшн Aluminium oxide-based sulphur recovery catalyst and method for production thereof
RU2668907C1 (en) * 2013-12-06 2018-10-04 Тиссенкрупп Индастриал Солюшнз Аг Method and plant for producing coke by treating sulphur-containing process residues from crude oil processing, petroleum coke formed from sulphur-containing process residues
RU2670759C2 (en) * 2013-09-12 2018-10-25 Джонсон Мэтти Каталистс (Джермани) Гмбх Catalyst and method for nitric oxide reduction in waste gas

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2531262A1 (en) * 2005-12-21 2007-06-21 Imperial Oil Resources Limited Very low sulfur heavy crude oil and process for the production thereof
JP4896766B2 (en) * 2006-02-24 2012-03-14 コスモ石油株式会社 Hydrocarbon desulfurization agent
US8557019B2 (en) * 2008-02-08 2013-10-15 Vale Inco Limited Process for production of nickel and cobalt using metal hydroxide, metal oxide and/or metal carbonate
CA2714575A1 (en) * 2008-02-08 2009-08-13 Vale Inco Limited Process for manufacturing prefluxed metal oxide from metal hydroxide and metal carbonate precursors
AU2009238168B2 (en) * 2008-04-16 2014-02-20 Vale Inco Limited Process for production of nickel and cobalt using metal hydroxide, metal oxide and/or metal carbonate
CN101618314B (en) * 2008-05-20 2013-03-06 中国石油化工股份有限公司 Desulfurizing adsorbent, preparation method and application thereof
CN101618313B (en) * 2008-06-30 2012-11-14 中国石油化工股份有限公司 Desulfurization adsorbent, preparation method and application thereof
RU2517639C2 (en) * 2008-12-31 2014-05-27 Чайна Петролеум & Кемикал Корпорейшн Adsorbent, method for production thereof and method of removing sulphur from cracked petrol or diesel fuel
JP5334630B2 (en) * 2009-03-06 2013-11-06 Jx日鉱日石エネルギー株式会社 Hydrocarbon oil desulfurization method and fuel cell system
WO2011052828A1 (en) * 2009-10-30 2011-05-05 한국전력공사 Zinc-based desulfurizing agent formed by spray drying method, and preparation method thereof
CA2944478A1 (en) 2011-07-20 2013-01-24 The Regents Of The University Of California Dual-pore device
FR2984762B1 (en) * 2011-12-21 2014-04-25 IFP Energies Nouvelles Catalytic adsorbent for capturing arsenic and selective hydrodesulfuration of catalytic cracking species
CN104549489B (en) * 2013-10-29 2017-07-25 中国石油化工股份有限公司 A kind of desulphurization catalyst and its preparation and the method for desulfurization of hydrocarbon oil
CN104148002B (en) * 2014-07-30 2017-07-11 迪普沃科技(深圳)有限公司 A kind of application of the Zr Ce O double-function catalyzing adsorbents and preparation method thereof with it in fuel desulfuration
CN105583001B (en) * 2014-10-20 2018-05-18 中国石油化工股份有限公司 A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN106554832A (en) * 2015-09-24 2017-04-05 刘从荡 A kind of preparation method of concave-convex bar methane desulfurizing dessicant
CN105749863A (en) * 2016-04-06 2016-07-13 山东成泰化工有限公司 Compound desulfurizer and preparation method thereof
CN107474870B (en) * 2016-06-07 2019-11-15 中国石油化工股份有限公司 A kind of vulcanization process of adsorbent

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2890178A (en) * 1953-10-14 1959-06-09 Exxon Research Engineering Co Hydrocarbon conversion catalysts
US2846363A (en) * 1954-09-29 1958-08-05 Pure Oil Co Catalysts for naphtha reforming
US2964463A (en) * 1956-12-10 1960-12-13 Pure Oil Co Upgrading hydrocarbon oils in the presence of hydrogen with a tungsten oxide, molybdenum oxide on silica-alumina catalyst composite
US3374183A (en) * 1961-03-30 1968-03-19 Ethyl Corp Copper oxide-alumina catalyst composition
US3104268A (en) * 1962-03-19 1963-09-17 Sinclair Research Inc Alkylation of aromatics with a zinc oxide, chromium oxide, copper oxide, silica-alumina catalyst
NL301436A (en) * 1962-12-12
GB1044333A (en) * 1963-04-01 1966-09-28 British Petroleum Co Hydrogenation process
GB1010574A (en) * 1963-04-23 1965-11-17 British Petroleum Co Production of hydrogen-containing gases
US3340012A (en) * 1963-12-19 1967-09-05 Universal Oil Prod Co Hydrogen production in a fluidized bed of attrition resistant catalyst
FR1413913A (en) * 1964-07-08 1965-10-15 Raffinage Cie Francaise Method and dehydrogenation catalyst aliphatic hydrocarbons
US3349025A (en) * 1965-07-15 1967-10-24 Gulf Research Development Co Hydrocracking with a presulfided tungsten oxide composite catalyst from the group comprising of silver, zinc or thorium on a siliceous carrier
US3447893A (en) * 1966-02-04 1969-06-03 Ethyl Corp Oxidation catalysts
US3625867A (en) * 1967-06-02 1971-12-07 Takachika Yoshino Process for production of metal oxide-antimony oxide catalysts
US3501418A (en) * 1967-07-14 1970-03-17 Grace W R & Co Process for preparing cracking catalysts
US3524721A (en) * 1967-12-22 1970-08-18 Ethyl Corp Catalyst composition
CA1021354A (en) * 1972-04-20 1977-11-22 Alvin B. Stiles Methanol synthesis catalyst
US4752623A (en) * 1984-07-30 1988-06-21 The Dow Chemical Company Mixed alcohols production from syngas
US4565800A (en) * 1985-06-24 1986-01-21 Philips Petroleum Company Hydrofining catalysts
US4596654A (en) * 1985-06-24 1986-06-24 Phillips Petroleum Company Hydrofining catalysts
US5045522A (en) * 1990-03-27 1991-09-03 Phillips Petroleum Company Absorption composition comprising zinc titanate for removal of hydrogen sulfide from fluid streams
US6254766B1 (en) 1999-08-25 2001-07-03 Phillips Petroleum Company Desulfurization and novel sorbents for same
US6676829B1 (en) * 1999-12-08 2004-01-13 Mobil Oil Corporation Process for removing sulfur from a hydrocarbon feed
US6274533B1 (en) * 1999-12-14 2001-08-14 Phillips Petroleum Company Desulfurization process and novel bimetallic sorbent systems for same
US6683024B1 (en) * 2000-03-15 2004-01-27 Conocophillips Company Desulfurization and novel sorbents for same
US6346190B1 (en) * 2000-03-21 2002-02-12 Phillips Petroleum Company Desulfurization and novel sorbents for same
JP4531917B2 (en) * 2000-03-31 2010-08-25 出光興産株式会社 Method for producing nickel-based desulfurization agent
JP4580070B2 (en) * 2000-03-31 2010-11-10 出光興産株式会社 Desulfurization agent for petroleum hydrocarbons and method for producing hydrogen for fuel cells
JP4388665B2 (en) * 2000-03-31 2009-12-24 出光興産株式会社 Ni-Cu desulfurizing agent and method for producing hydrogen for fuel cell
JP4580071B2 (en) * 2000-03-31 2010-11-10 出光興産株式会社 Desulfurization agent for petroleum hydrocarbons and method for producing hydrogen for fuel cells
JP4531939B2 (en) * 2000-03-31 2010-08-25 出光興産株式会社 Method for producing nickel-copper desulfurization agent
EP1270069B1 (en) * 2000-03-31 2011-06-15 Idemitsu Kosan Co., Ltd. Use of a desulfurizing agent
US6429170B1 (en) * 2000-05-30 2002-08-06 Phillips Petroleum Company Sorbents for desulfurizing gasolines and diesel fuel
AU8512301A (en) * 2000-08-31 2002-03-13 Phillips Petroleum Co Desulfurization and novel sorbents for same
US7105140B2 (en) * 2002-03-04 2006-09-12 Conocophillips Company Desulfurization compositions
US6878669B2 (en) * 2002-12-23 2005-04-12 Conocophillips Company Desulfurization and sorbent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2559627C2 (en) * 2012-06-12 2015-08-10 Чайна Петролеум Энд Кемикал Корпорейшн Aluminium oxide-based sulphur recovery catalyst and method for production thereof
RU2670759C2 (en) * 2013-09-12 2018-10-25 Джонсон Мэтти Каталистс (Джермани) Гмбх Catalyst and method for nitric oxide reduction in waste gas
RU2668907C1 (en) * 2013-12-06 2018-10-04 Тиссенкрупп Индастриал Солюшнз Аг Method and plant for producing coke by treating sulphur-containing process residues from crude oil processing, petroleum coke formed from sulphur-containing process residues

Also Published As

Publication number Publication date
EP1799794A4 (en) 2010-06-09
EP1799794A2 (en) 2007-06-27
BRPI0514299B1 (en) 2016-03-29
US20050020446A1 (en) 2005-01-27
WO2006020642A2 (en) 2006-02-23
CN101432398A (en) 2009-05-13
RU2007108545A (en) 2008-09-20
BRPI0514299A (en) 2008-06-10
JP2008510035A (en) 2008-04-03
CN101432398B (en) 2012-03-28
WO2006020642A3 (en) 2009-06-04

Similar Documents

Publication Publication Date Title
AU2009213825B2 (en) Absorbents
Wang et al. The enhanced adsorption of dibenzothiophene onto cerium/nickel-exchanged zeolite Y
JP4570307B2 (en) Method for producing sorbent for desulfurization and method for removing sulfur using sorbent for desulfurization using the same
US20060211906A1 (en) Method for purifying a liquid medium
CN1130253C (en) Sorbent composition, process for producing same and use in desulfurization
JP4532804B2 (en) Desulfurization process and new bimetallic sorbent system for it
CA2667887C (en) Process for adsorption of sulfur compounds from hydrocarbon streams
US6482314B1 (en) Desulfurization for cracked gasoline or diesel fuel
CN1048418C (en) Fluidizable sulfur sorbent and fluidized sorption method
US6683024B1 (en) Desulfurization and novel sorbents for same
CN1382201B (en) Desulfurization method and novel sorbents for same
HU228331B1 (en) Desulfurization and sorbents for same
JPH05192587A (en) Hydrogenation catalyst
US6992041B1 (en) Deep desulfurization catalyst, method for preparing the same and method for desulfurization using the same
US6346190B1 (en) Desulfurization and novel sorbents for same
CA2481527C (en) Desulfurization and sorbents for same
SK286585B6 (en) Hydroprocessing catalyst and use thereof
US20040262200A1 (en) Desulfurization with octane enhancement
US7160438B2 (en) Process for removal of nitrogen containing contaminants from gas oil feedstreams
US6930074B2 (en) Desulfurization and sorbent for the same
US20040129607A1 (en) Desulfurization and novel sorbents for same
US7087156B2 (en) Process for removal of nitrogen containing contaminants from gas oil feedstreams
US6635795B2 (en) Desulfurization with improved sorbent regeneration
JP2006512430A (en) Hydrotreating hydrocarbons using a mixture of catalysts
US6914033B2 (en) Desulfurization and novel compositions for same

Legal Events

Date Code Title Description
PC4A Invention patent assignment

Effective date: 20101029