CN104557388A - Deep desulfurization method of refinery C4 - Google Patents
Deep desulfurization method of refinery C4 Download PDFInfo
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Abstract
The invention discloses a deep desulfurization method of refinery C4, which comprises the following steps that at least two fixed bed reactors are adopted; a C4 fraction is subjected to adsorption desulfurization by the action of an adsorbent loaded with a hydrogenated active component; the C4 fraction is switched to another reactor for the adsorption desulfurization after adsorption saturation; hydrogen is supplied to the adsorption saturated fixed bed reactor for a hydrogenated desulfurization reaction; and the adsorbent loaded with the hydrogenated active component is regenerated. Refinery C4 desulfurized by the method can directly serve as a raw production material of MTBE (methyl tert-butyl ether), and isobutylene in the C4 fraction is sufficiently protected and utilized.
Description
Technical field
The invention belongs to the desulfurization technology of refinery C four, relate in particular to a kind of process for deep desulphurization of refinery C four.
Background technology
Be utilize iso-butylene wherein to produce methyl tertiary butyl ether (MTBE) as gasoline blending component in China's refinery C four main application, after ether, carbon four uses further as domestic fuel or industrial chemicals.
In petroleum refining process, the refinery C four that the devices such as coking, Atmospheric vacuum, catalytic cracking produce, containing a large amount of sulfide, except H
2outside S, also has the organosulfur of various form, as COS, CH
3sH, C
2h
5sH, CH
3sCH
3deng, wherein mainly CH
3sH.The existence of these sulphur can cause the poisoning and inactivation of catalyzer in following process process, causes very adverse influence to aspects such as derived product processing, environment protection and corrosion protection of equipment.Wherein the most urgent is improving constantly along with China's standard of fuel, and as Beijing provincial standard after adjustment in 2012, substantially integrate with the standard of Europe with the stage, for sulphur content index, Beijing and Europe are all 10 μ gg
-1, the U.S. is 15 μ gg
-1.Because the sulphur content of refinery C four exceeds standard, the MTBE sulphur content that to cause with refinery C four be raw material production significantly increases, and has exceeded the requirement of gasoline standard, and has been difficult to add in gasoline.If refinery C four is as industrial chemicals in addition, downstream deep-processing process is then tighter to the requirement of sulphur content.Therefore, the sulfide in deep removal refinery C four, has important economy and environment protection significance.
The method of usual refinery C four desulfurization is a lot, and the kind for sulfocompound is different with content, and method is also different, and that industrially applies mainly contains dry method and the large class of wet method two.Dry method is applicable to sulphur content is low or treatment capacity is little refinery C four desulfurization and adopts, as with zinc oxide, aluminum oxide, charcoal absorption or absorb with simple alkaline process; The process of the refinery C four that, treatment capacity high for sulphur content is large is divided into 2 steps: (1) utilizes alkali lye to remove hydrogen sulfide in refinery C four, or removes in the lump after being hydrolyzed by COS, and conventional alkali lye is alkanolamine solution and corresponding combination solution; (2) adopt the alkali lye alkali cleaning containing cobalt sulfonated phthalocyanine, the mode of alkali cleaning can be extracting, Mei Luokesi (Merox) the extracting and oxidizing method that tunica fibrosa technology also can be adopted to propose as USP4124494, USP4159964, CN85103718.Although above-mentioned oxidation extraction desulfurization alcohol technology can significantly improve the solubleness of mercaptan in alkali lye, improve Mercaptan removal rate, but this method still there is shortcoming as follows: (1) Cobalt Phthalocyanine class catalyzer is in alkali phase, easily assembles inactivation, cause frequent more catalyst changeout, catalyzer cost is quite high; (2) alkali lye that refinery C four-function contains catalyzer carries out mercaptan extracting, and under catalyzer existence condition, sodium mercaptides easily generates disulphide and is brought in refining refinery C four-product, and cause desulfurization degree low, refinery C four total sulfur content exceeds standard; (3) environmental protection pressure has been increased the weight of owing to employing caustic alkali, because caustic alkali is serious for environmental pollution, for reducing the discharge of waste lye, ammoniacal liquor is adopted to replace caustic liquid alkali to carry out refinery C four caustic prescrub, use air-lift device process ammoniacal liquor, make ammonia regeneration and recycle, but then must increase gas device like this, and ammoniacal liquor alkalescence is more weak, organosulfur is difficult to wash-out.Also useful solid alkali replaces liquid caustic soda to wash, then is mixed into deodorization after deodorizing tower with promoting agent, but need add special deodorizing composition, adds desulphurization cost and sweetening effectiveness is undesirable.
We know that hydrogenating desulfurization is effective, the cleaning method that remove sulfide in petroleum hydrocarbon, but the hydrogenating desulfurization for refinery C four is difficult to realize usually, this is because C 4 olefin hydrogenation activity is wherein far above the hydrodesulfurization activity of organosulfur compound in refinery C four, hydrodesulfurization process seriously can change the composition of refinery C four, a large amount of iso-butylenes is saturated, and loses the function of etherificate synthesis MTBE.Have employed in CN1900232A with aluminum oxide is carrier, cobalt, the Hydrobon catalyst of molybdenum bimetallic active component is to the liquefied gas extracting propylene, the refinery C four of butene component carries out hydrogenating desulfurization low sulfur content, temperature of reaction is 145 ~ 300 DEG C, hydrogen dividing potential drop is 1.0 ~ 2.0MPa, during liquid, volume space velocity is 1.0 ~ 5.0, the method adopts the method for extracting to isolate alkene, residual a large amount of alkene still can by hydrotreated lube base oil, cause olefin loss, extractive process flow process is tediously long in addition, and solvent needs manipulation of regeneration, adds processing cost.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of process for deep desulphurization of refinery C four.Refinery C four after desulfurization can directly as the raw materials for production of MTBE, and the iso-butylene in C-4-fraction is adequately protected and utilizes.
A kind of process for deep desulphurization of refinery C four, comprise following content: adopt fixed-bed reactor, described fixed-bed reactor are at least two, first C-4-fraction carries out adsorption desulfurize under the effect of the sorbent material of load hydrogenation active component, adsorb saturated after C-4-fraction switched to another reactor proceed adsorption desulfurize, and in the saturated fixed-bed reactor of absorption, pass into hydrogen carry out hydrodesulfurization reaction the sorbent material of load hydrogenation active component is regenerated.
In the inventive method, described adsorption desulfurize condition is as follows: temperature 50 ~ 200 DEG C; Pressure 1.0 ~ 5.0MPa; Refinery C four air speed 1 ~ 10h
-1.
In the inventive method, described hydrodesulfurization reaction condition is as follows: temperature 150 ~ 280 DEG C; Pressure 2.5 ~ 5.0MPa; Hydrogen gas space velocity 100 ~ 2000h
-1, 8 ~ 24 hours reaction times.
In the inventive method, the sorbent material specific surface area of described load hydrogenation active component is 120 ~ 350m
2/ g, pore volume is 0.10 ~ 0.30 cm
3/ g, tap density is 0.70 ~ 0.95g/cm
3.The content of the sorbent material Middle molecule sieve of load hydrogenation active component is by weight 60 ~ 90%, and the content of alumina supporter is 9 ~ 39%, and hydrogenation metal active ingredient is surplus.Described molecular sieve refers to the molecular sieve with adsorption function, be selected from but be not limited to following molecular sieve: one or more in Si-Al molecular sieve, silicoaluminophosphamolecular molecular sieves, being preferably beta-molecular sieve, ZSM Series Molecules sieve, mordenite, faujusite, erionite, type A zeolite, MCM Series Molecules sieve, SAPO Series Molecules sieve in one or more.ZSM Series Molecules sieve can be one or more in ZSM-5, ZSM-8, ZSM-11, ZSM-35.SAPO Series Molecules sieve can be one or more in SAPO-5, SAPO-11.MCM Series Molecules sieve can be one or more in MCM-22, MCM-41 molecular sieve.One or more more preferably in ZSM-5 molecular sieve, mordenite, Y zeolite, the best is ZSM-5 molecular sieve.Described hydrogenation active metals component is VIII race or VI B race metal, and as platinum, palladium, one or several in cobalt, molybdenum, nickel, tungsten, are preferably cobalt, molybdenum, nickel, tungsten.
In the inventive method, also containing appropriate metal promoter in the sorbent material of described load hydrogenation active component, described metal promoter refers to one or more in zirconium, zinc, copper, cerium, and weight content is 2 ~ 7%.The adsorption function that the adding of auxiliary agent can improve sorbent material and saturated after the hydrogenating desulfurization efficiency of sorbent material, improve absorption and the regenerability of sorbent material.
In the inventive method, the sorbent material of described load hydrogenation active component is adopted and is prepared with the following method: kneading and compacting is carried out in selected molecular sieve, tackiness agent, peptizing agent, extrusion aid mixing, shaping back loading hydrogenation active component or load active component and metal promoter, the sorbent material of obtained load hydrogenation active component after drying roasting.Wherein said tackiness agent refers to activated alumina or its precursor; Described peptizing agent be mineral acid, organic acid, strong acid cation ion salt as aluminum nitrate, mineral acid can be nitric acid, hydrochloric acid, sulfuric acid, and organic acid can be one or more in formic acid, acetic acid, oxalic acid, citric acid etc.Described extrusion aid refers to the material that can help aluminum oxide extrusion molding, as carbon black, field mountain valley with clumps of trees and bamboo powder, Graphite Powder 99, citric acid etc.
A kind of there is absorption and the integrated sorbent material of hydrogenating function by the surprised discovery of research contriver by preparing, and after utilizing the adsorption function of sorbent material that the sulfide in carbon Four composition is separated separately, carry out hydrotreatment again, just namely can carry out hydrogenating desulfurization to refinery C four desulfurization, its composition can not be changed again, keep iso-butylene content constant.
The sorbent material that the inventive method obtains is applied in refinery C four hydrodesulfurization process of fixed-bed process, sweetening effectiveness is excellent, adsorbent reactivation process is simply effective, both change direct hydrogenation desulfurization can having been avoided to cause refinery C four form, the hydrogenating desulfurization clean to refinery C four can be realized again, the secondary pollutants such as the alkaline residue avoiding conventional desulfurization process to produce.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail; following examples do not form limiting the scope of the invention; those skilled in the art is in conjunction with specification sheets of the present invention and can do suitable expansion in full, and these expansions should be all protection scope of the present invention.In the inventive method, specific surface area and pore volume adopt low temperature liquid nitrogen determination of adsorption method.Analysis of sulfur content adopts coulomb Sulfur Analysis method.
In the inventive method, the concrete preparation process of the sorbent material of described load hydrogenation active component is as follows: appropriate aluminum oxide and aqueous nitric acid are mixed, obtained tackiness agent, add ZSM-5 zeolite, extrusion aid in proportion, kneading is even, extruded moulding, wet bar at 90 ~ 130 DEG C dry 6 ~ 12 hours, again through 480 ~ 650 DEG C of roastings 2 ~ 6 hours, obtained carrier.Carrier, the aqueous impregnation containing a certain amount of tungsten salt and nickel salt 1 ~ 4 hour, filters, dry (80 ~ 120 DEG C, 6 ~ 12), roasting (480 ~ 650 DEG C, 2 ~ 6 hours), then carries out double-steeping at the metal promoter aqueous solution, dipping time 1 ~ 4 hour, filter, dry (80 ~ 120 DEG C, 6 ~ 12), roasting (480 ~ 650 DEG C, 2 ~ 6 hours) obtains finished catalyst.Tungsten salt used is ammonium metawolframate, and nickel salt used is nickelous nitrate.Metal promoter used is cupric nitrate, zinc nitrate, zirconium nitrate, cerous nitrate.
Embodiment 1
Get aluminum oxide (specific surface area 330 m
2/ g, pore volume 0.75 cm
3/ g) 85.0g, add 73.0g distilled water and 10.5ml concentrated nitric acid, mix, cook composite adhesives.Getting HZSM-5(silica alumina ratio is 50) 145.5g, field mountain valley with clumps of trees and bamboo powder 4.0g and above-mentioned tackiness agent kneading, extruded moulding, wet bar at 120 DEG C dry 4 hours, at 550 DEG C, roasting 5 hours, makes sorbent material.Get 47.5g ammonium metawolframate and 51.2g nickelous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned sorbent material is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, roasting 3 hours at 550 DEG C, then carry out double-steeping, get 32.2g five water zirconium nitrate, 23.3g zinc nitrate hexahydrate, dissolve with distilled water, be made into 200ml solution, above-mentioned sorbent material is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, at 550 DEG C, roasting 3 hours, makes the adsorbent A of load hydrogenation active component.
The adsorbent A 100ml of the above-mentioned load hydrogenation active component prepared is loaded in fixed-bed reactor, temperature of reaction 50 DEG C, reaction pressure 2.5MPa, air speed (refinery C four), 2.0h
-1condition under, adopt sulphur content to be that the refinery C four of 450ppm carries out adsorption desulfurize for raw material, raw material mainly form all adopt identical raw material in Table 1(following examples), the sulphur in refinery C four is adsorbed on bed.After the adsorbent of load hydrogenation active component is saturated, switch to another reactor and carry out adsorption desulfurize, simultaneously in the reactor after saturated, introduce hydrogen, temperature of reaction 180 DEG C, pressure 2.5MPa, under the condition of air speed (hydrogen) 300h-1, carries out gas phase hydrogenation regeneration in 16 hours to the sorbent material of load hydrogenation active component, after hydrogenation tail gas desulfurization hydrogen, hydrogen sulfide enters Cross unit process.Desulfurization results after the adsorbent reactivation of desulfurization results and load hydrogenation active component is in table 2, table 3.
Table 1
Embodiment 2
Get aluminum oxide (specific surface area 310 m
2/ g, pore volume 0.96 cm
3/ g) 85.0g, add 73.0g distilled water and 10.5ml concentrated nitric acid, mix, cook composite adhesives.Getting HZSM-5(silica alumina ratio is 25) 145.5g, field mountain valley with clumps of trees and bamboo powder 3.0g and above-mentioned tackiness agent kneading, extruded moulding, wet bar at 120 DEG C dry 4 hours, at 550 DEG C, roasting 5 hours, makes carrier.Get 31.6g ammonium metawolframate and 25.6g nickelous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, at 550 DEG C, roasting 3 hours, then carries out double-steeping, get 27.6g zinc nitrate hexahydrate and 14.4g six water cerous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, at 550 DEG C, roasting 3 hours, makes the adsorbent B of load hydrogenation active component.
The adsorbent B 100ml of the above-mentioned load hydrogenation active component prepared is loaded in fixed-bed reactor, temperature of reaction 100 DEG C, reaction pressure 5.0MPa, air speed (refinery C four), 1.0h
-1condition under, adopt sulphur content to be that the refinery C four of 150ppm carries out adsorption desulfurize for raw material, the sulphur in refinery C four be adsorbed on bed.After the adsorbent of load hydrogenation active component is saturated, switches to another reactor and carry out adsorption desulfurize, simultaneously in the reactor after saturated, introduce hydrogen, temperature of reaction 200 DEG C, pressure 5.0MPa, air speed (hydrogen) 1000h
-1condition under, carry out the regeneration of 24 hours gas phase hydrogenations to the sorbent material of load hydrogenation active component, after hydrogenation tail gas desulfurization hydrogen, hydrogen sulfide enters Cross unit process.Desulfurization results after the adsorbent reactivation of desulfurization results and load hydrogenation active component is in table 2, table 3.
Embodiment 3
Get aluminum oxide (specific surface area 330 m
2/ g, pore volume 0.75 cm
3/ g) 85.0g, add 73.0g distilled water and 10.5ml concentrated nitric acid, mix, cook composite adhesives.Getting HZSM-5(silica alumina ratio is 80) 145.5g, field mountain valley with clumps of trees and bamboo powder 3.0g and above-mentioned tackiness agent kneading, extruded moulding, wet bar at 120 DEG C dry 4 hours, at 550 DEG C, roasting 5 hours, makes carrier.Get 62.4g ammonium molybdate and 34.1g nickelous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, at 550 DEG C, roasting 3 hours, then carries out double-steeping, get 15.6g nitrate trihydrate copper and 20.5g six water cerous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, roasting 3 hours at 550 DEG C, makes the sorbent material C of load hydrogenation active component.
The sorbent material C100ml of the above-mentioned load hydrogenation active component prepared is loaded in fixed-bed reactor, temperature of reaction 100 DEG C, reaction pressure 2.5MPa, air speed (refinery C four), 3.0h
-1condition under, adopt sulphur content to be that the refinery C four of 300ppm carries out adsorption desulfurize for raw material, the sulphur in refinery C four be adsorbed on bed.After the adsorbent of load hydrogenation active component is saturated, switches to another reactor and carry out adsorption desulfurize, simultaneously in the reactor after saturated, introduce hydrogen, temperature of reaction 150 DEG C, pressure 2.5MPa, air speed (hydrogen) 500h
-1condition under, carry out the regeneration of 20 hours gas phase hydrogenations to the sorbent material of load hydrogenation active component, after hydrogenation tail gas desulfurization hydrogen, hydrogen sulfide enters Cross unit process.Desulfurization results after the sorbent material activation of desulfurization results and load hydrogenation active component is in table 2, table 3.
Embodiment 4
Get aluminum oxide (specific surface area 330 m
2/ g, pore volume 0.75 cm
3/ g) 85.0g, add 73.0g distilled water and 10.5ml concentrated nitric acid, mix, cook composite adhesives.Get Y zeolite (SiO
2: Al
2o
3>=5) 145.5g, field mountain valley with clumps of trees and bamboo powder 3.0g and above-mentioned tackiness agent kneading, extruded moulding, wet bar at 120 DEG C dry 4 hours, at 650 DEG C, roasting 5 hours, makes carrier.Get 31.6g ammonium metawolframate and 25.6g nickelous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, at 550 DEG C, roasting 3 hours, then carries out double-steeping, get 13.6g nitrate trihydrate copper and 20.1g zinc nitrate hexahydrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, roasting 3 hours at 550 DEG C, makes the sorbent material D of load hydrogenation active component.
The sorbent material 100ml of the above-mentioned load hydrogenation active component prepared is loaded in fixed-bed reactor, temperature of reaction 150 DEG C, reaction pressure 3.0MPa, air speed (refinery C four), 2.0 h
-1condition under, adopt sulphur content to be that the refinery C four of 300ppm carries out adsorption desulfurize for raw material, the sulphur in refinery C four be adsorbed on bed.After the adsorbent of load hydrogenation active component is saturated, switches to another reactor and carry out adsorption desulfurize, simultaneously in the reactor after saturated, introduce hydrogen, temperature of reaction 150 DEG C, pressure 3.0MPa, air speed (hydrogen) 100h
-1condition under, carry out the regeneration of 24 hours gas phase hydrogenations to the sorbent material of load hydrogenation active component, after hydrogenation tail gas desulfurization hydrogen, hydrogen sulfide enters Cross unit process.Desulfurization results after the adsorbent reactivation of desulfurization results and load hydrogenation active component is in table 2, table 3.
Embodiment 5
Get aluminum oxide (specific surface area 330 m
2/ g, pore volume 0.75 cm
3/ g) 85.0g, add 73.0g distilled water and 10.5ml concentrated nitric acid, mix, cook composite adhesives.Get 13X zeolite (SiO
2: Al
2o
3>=5) 145.5g, field mountain valley with clumps of trees and bamboo powder 3.0g and above-mentioned tackiness agent kneading, extruded moulding, wet bar at 120 DEG C dry 4 hours, at 650 DEG C, roasting 5 hours, makes carrier.Get 31.6g ammonium metawolframate and 25.6g nickelous nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, at 550 DEG C, roasting 3 hours, then carries out double-steeping, get 17.5g six water cerous nitrate and 23.2g five water zirconium nitrate distilled water dissolves, be made into 200ml solution, above-mentioned carrier is added in steeping fluid, flood 2 hours, then filter, drying 4 hours at 110 DEG C, roasting 3 hours at 550 DEG C, makes the sorbent material E of load hydrogenation active component.
The sorbent material E100ml of the above-mentioned load hydrogenation active component prepared is loaded in fixed-bed reactor, temperature of reaction 50 DEG C, reaction pressure 1.5MPa, air speed (refinery C four), 2.0h
-1condition under, adopt sulphur content to be that the refinery C four of 100ppm carries out adsorption desulfurize for raw material, the sulphur in refinery C four be adsorbed on bed.After the adsorbent of load hydrogenation active component is saturated, switches to another reactor and carry out adsorption desulfurize, simultaneously in the reactor after saturated, introduce hydrogen, temperature of reaction 180 DEG C, pressure 1.5MPa, air speed (hydrogen) 700h
-1condition under, carry out the regeneration of 15 hours gas phase hydrogenations to the sorbent material of load hydrogenation active component, after hydrogenation tail gas desulfurization hydrogen, hydrogen sulfide enters Cross unit process.Desulfurization results after the adsorbent reactivation of desulfurization results and load hydrogenation active component is in table 2, table 3.
Table 2
Table 3
Claims (10)
1. the process for deep desulphurization of a refinery C four, it is characterized in that: comprise following content: adopt fixed-bed reactor, described fixed-bed reactor are at least two, first C-4-fraction carries out adsorption desulfurize under the effect of the sorbent material of load hydrogenation active component, adsorb saturated after C-4-fraction switched to another reactor proceed adsorption desulfurize, and in the saturated fixed-bed reactor of absorption, pass into hydrogen carry out hydrodesulfurization reaction the sorbent material of load hydrogenation active component is regenerated.
2. method according to claim 1, is characterized in that: described adsorption desulfurize condition is as follows: temperature 50 ~ 200 DEG C; Pressure 1.0 ~ 5.0MPa; Refinery C four air speed 1 ~ 10h
-1.
3. method according to claim 1, is characterized in that: described hydrodesulfurization reaction condition is as follows: temperature 150 ~ 280 DEG C; Pressure 2.5 ~ 5.0MPa; Hydrogen gas space velocity 100 ~ 2000h
-1, 8 ~ 24 hours reaction times.
4. method according to claim 1, is characterized in that: the sorbent material specific surface area of described load hydrogenation active component is 120 ~ 350m
2/ g, pore volume is 0.10 ~ 0.30 cm
3/ g, tap density is 0.70 ~ 0.95g/cm
3, the content of the sorbent material Middle molecule sieve of load hydrogenation active component is by weight 60 ~ 90%, and the content of alumina supporter is 9 ~ 39%, and hydrogenation metal active ingredient is surplus.
5. method according to claim 1, it is characterized in that: described molecular sieve refers to the molecular sieve with adsorption function, be selected from but be not limited to following molecular sieve: beta-molecular sieve, ZSM Series Molecules sieve, mordenite, faujusite, erionite, type A zeolite, MCM Series Molecules sieve, SAPO Series Molecules sieve in one or more.
6. method according to claim 5, it is characterized in that: ZSM Series Molecules sieve is one or more in ZSM-5, ZSM-8, ZSM-11, ZSM-35, SAPO Series Molecules sieve is one or more in SAPO-5, SAPO-11, and MCM Series Molecules sieve is one or more in MCM-22, MCM-41 molecular sieve.
7. method according to claim 5, is characterized in that: described molecular sieve is one or more in ZSM-5 molecular sieve, mordenite, Y zeolite.
8. method according to claim 1, is characterized in that: described hydrogenation active metals component comprises platinum, palladium, one or several in cobalt, molybdenum, nickel, tungsten.
9. method according to claim 1, is characterized in that: also containing appropriate metal promoter in the sorbent material of described load hydrogenation active component, described metal promoter refers to one or more in zirconium, zinc, copper, cerium, and weight content is 2 ~ 7%.
10. method according to claim 1, it is characterized in that: the sorbent material of described load hydrogenation active component is adopted and prepared with the following method: kneading and compacting is carried out in selected molecular sieve, tackiness agent, peptizing agent, extrusion aid mixing, shaping back loading hydrogenation active component or load active component and metal promoter, the sorbent material of obtained load hydrogenation active component after drying roasting.
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| CN108295809B (en) * | 2018-02-05 | 2020-12-11 | 中国海洋石油集团有限公司 | Composite desulfurization adsorbent and preparation method and application thereof |
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