CN104998657A - Catalyst for refined removal of trace amount of sulfides in benzene and its preparation method and use - Google Patents

Catalyst for refined removal of trace amount of sulfides in benzene and its preparation method and use Download PDF

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CN104998657A
CN104998657A CN201510367391.5A CN201510367391A CN104998657A CN 104998657 A CN104998657 A CN 104998657A CN 201510367391 A CN201510367391 A CN 201510367391A CN 104998657 A CN104998657 A CN 104998657A
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catalyst
benzene
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CN104998657B (en
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王艳辉
张羿新
唐劲松
王建伟
陈恩之
姜曦
张远洋
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Shanghai Huafon New Material Research & Development Technology Co Ltd
Chongqing Huafeng Chemical Co Ltd
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Shanghai Huafon New Material Research & Development Technology Co Ltd
Chongqing Huafeng Chemical Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a catalyst for refined removal of a trace amount of sulfides in benzene and its preparation method and use. The catalyst has a general formula of Ru-M/Al2O3. The preparation method comprises that Al2O3 as a carrier is loaded with 0.5-5.0% by mass of Ru as an active component and 3.0-16.0% by mass of M as an active component by a program impregnation method, wherein M represents one or more of Fe, Cu and Zn. The prepared catalyst can be used for refined removal of a trace amount of sulfides such as thiophene-type sulfides. The loaded catalyst is free of precious metal palladium so that a cost is reduced. The catalyst realizes ppb level refined removal of a trace amount of thiophene-type sulfides in benzene, has a high sulfur capacity, a long service life, good selectivity, no pollution and renewability and can be widely used in a benzene hydrogenation reaction pretreatment process.

Description

Essence removes Catalysts and its preparation method and the application of trace sulfide in benzene
Technical field
The invention belongs to environmental protection and chemical technology field; relate to Catalysts and its preparation method and application that a kind of essence removes trace sulfide in benzene, relate generally to a kind of essence and remove loaded catalyst of the thiophene-type sulfide of trace in benzene and its preparation method and application.
Background technology
Cyclohexene is a kind of important organic synthesis intermediate, and to adopt benzene selective hydrogenation directly to prepare cyclohexene be at present the most feasible economically technology path.Because benzene hydrogenation process generally all uses noble metal catalyst, in benzene, the sulfide of trace can cause noble metal catalyst slow poisoning, thus make the conversion ratio of benzene selective hydrogenation course of reaction and selectively to decline gradually, until catalyst complete deactivation, and the activity and selectivity of regenerated catalyst cannot return to the initial performance of fresh catalyst.For the service life of extending catalyst, course of reaction need be raw material with highly purified benzene, and wherein sulfur content requires to be reduced to ppb level.
Petrobenzene is the accessory substance in oil refining process catalytic reforming reaction, because of the thiophenes of petrobenzene and the boiling point of benzene close, be difficult to it to separate completely by conventional distillation method, therefore the sulfide of petrobenzene more or less containing some, traditional hydrodesulfurizationprocess process adopts such as aluminium oxide to be carrier, load W, Ni, Mo etc. are the catalyst of active constituent, under the condition of higher hydrogen oil ratio and reaction temperature, organic sulfur compound in benzene is changed into inorganic sulphide, because this course of reaction is by the restriction on thermodynamics, total sulfur content in benzene feedstock is difficult to be down to ppb level.In addition, as adopted the method for azeotropic distillation, thiophenes can be realized in theory to be separated with benzene, not only can obtain purified petroleum benzin, but also can thiophenes have been obtained, but the method be only applicable to sulfide content in benzene higher when, and for total sulfur content be the benzene feedstock of ppm level, adopting the method for azeotropic distillation to be separated sulfide wherein, is all infeasible economically and technically.Compare with above-mentioned and other sulfur method, catalytic adsorption method is the method for removing trace sulfide in benzene the most suitable, and the key realizing this process adopts efficient catalytic adsorption desulphurization catalyst.
CN101612549A discloses a kind of with γ-Al 2o 3for carrier, Ag 2o and CeO 2for the catalyst of active constituent, for removing thiophene in coking benzene and CS 2.Under normal pressure, room temperature condition, the thiophene in coking benzene can be removed to below 20ppm from 500ppm, simultaneously can by the CS in coking benzene 2be removed to below 1ppm from 200ppm, but be difficult to realize the sulfide in benzene to be removed to ppb level.
CN103480325A discloses one and palladium is dissolved in organic solvent, adopts the Pd/Al for removing benzene medium sulphide content prepared by infusion process 2o 3desulphurization catalyst, can be down to ppb level by the sulfide in refining benzene from ppm level under experiment condition.
The above-mentioned published catalyst removing benzene medium sulphide content for catalytic adsorption, or be difficult to realize the sulfide in benzene to be removed to ppb level under cryogenic, thus cannot be applied to benzene selective hydrogenation technical process; Be adopt precious metals pd as main active constituent, because precious metal palladium is expensive, will significantly increase the production cost of benzene selective hydrogenation process.And at present, in prior art, not yet openly performance quite or better can be used for substituting the loaded catalyst adopting precious metals pd as the catalyst of main active constituent.
Summary of the invention
The invention provides the catalyst that a kind of essence removes trace sulfide in benzene, this catalyst is loaded catalyst, and the present invention also provides the preparation method of this loaded catalyst and the purposes for removing benzene medium sulphide content particularly thiophene-type sulfide thereof simultaneously.
Loaded catalyst of the present invention is by adopting γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3powder mixed-forming prepares the Al of function admirable 2o 3carrier, and adopt program infusion process load base metal and the desulphurizing activated component of noble metal respectively, prereduction is carried out to the catalyst precursor of preparation, prepare a kind of catalyst removing trace sulfide in benzene in catalytic adsorption mode, this catalyst has very high selective catalysis adsorption desulfurize performance, and the sulfide of trace in benzene can be realized to be reduced to ppb level from ppm level.Catalyst of the present invention can be widely used in the raw material pretreatment process process of benzene hydrogenation especially benzene selective hydrogenation, the serviceability of protection benzene hydrogenating catalyst, thus extends the service life of catalyst in benzene hydrogenation process.
A kind of essence provided by the invention removes the catalyst of trace sulfide in benzene, and its general formula is Ru-M/Al 2o 3, this catalyst comprises carrier and load active component on the carrier, and described carrier is Al 2o 3carrier, described active component is made up of noble metal active component Ru and base metal active component M, wherein M is one or more in Fe, Cu, Zn, the mass content of described noble metal active component ruthenium accounts for whole catalyst quality 0.5 ~ 5.0%, and the mass content of described base metal active component M accounts for whole catalyst quality 3.0 ~ 16.0%.
Above-mentioned essence provided by the invention removes the catalyst of trace sulfide in benzene, using noble metal active component Ru and base metal active component M jointly as catalyst activity component, thus instead of the palladium of cost intensive, reduces the cost of material of catalyst.And, because the catalytic activity impact of the synergy between active constituent on catalyst is very large, therefore only suitable active constituent and suitable proportioning is selected according to technique scheme of the present invention, the synergy of each active constituent of competence exertion, thus ensure the catalytic performance that catalyst has had.
Essence of the present invention removes the catalyst of trace sulfide in benzene under fixed bed reaction condition, at 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, benzene liquid volume air speed 0.5 ~ 4.0h -1, benzene feed is under the condition of the ppm order of magnitude containing thiophene, the Sulfur capacity>=0.6g thiophene/Kg catalyst of described catalyst.
Catalyst carrier of the present invention can select conventional Al 2o 3carrier, but in a preferred embodiment of the invention, described carrier is for containing γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3mixing Al 2o 3carrier.Further preferably, 40 ~ 70% γ type Al are contained in described carrier 2o 3, 20 ~ 50% ρ type Al 2o 3with 20 ~ 50% α type Al 2o 3, the cylindrical particle that described carrier specification is φ 1.5 ~ 2.5mm, length is 2 ~ 3mm.When removing the thiophene-type sulfide in benzene owing to adopting chemiadsorption, the surface acidic-basic property of catalyst is very large to the performance impact of catalyst, and catalyst of the present invention adopts γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3powder by a certain percentage mixed-forming prepares alumina carrier, effectively can regulate the Acidity of Aikalinity of preparation-obtained catalyst surface, thus the catalytic adsorption essence preparing more excellent performance removes the catalyst of micro-thiophene-type sulfide in benzene.Meanwhile, the present invention adopts γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3alumina carrier required for powder mixed-forming preparation by a certain percentage, the content that can also adjust the alumina powder of variant crystal formation according to actual needs, to prepare the catalyst of various varying strength, better meets the demand of differential responses process.
Present invention also offers the preparation method that a kind of above-mentioned essence removes the catalyst of trace sulfide in benzene, comprise the following steps:
(1) adopt program infusion process successively at described Al 2o 3the presoma of supported on carriers base metal active constituent M and noble metal active component Ru, obtains catalyst precursor;
(2) after under fixed bed reaction condition, 200 ~ 450 DEG C, gas volume air speed is 600 ~ 1500h -1, H 2/ N 2volume ratio is under the condition of 0.4 ~ 1.5:1, pressure 0.1 ~ 0.4MPa, carries out pre-activate 2 ~ 6 hours to described catalyst precursor, obtains the catalyst that described essence removes trace sulfide in benzene.
Preferably, also comprised before described step (1): prepare described Al by the following method 2o 3carrier:
First, by graphite, sesbania powder, 300 ~ 400 object γ type Al 2o 3powder, ρ type Al 2o 3powder and α type Al 2o 3powder mixes and obtains powder mixture, wherein γ type Al 2o 3powder 40 ~ 70%, ρ type Al 2o 3powder 20 ~ 50%, α type Al 2o 3powder 20 ~ 50%, graphite 1 ~ 4%, sesbania powder 1 ~ 4%;
Then, be 1 ~ 4% of described powder mixture quality by quality, concentration be 45 ~ 63% salpeter solution to add quality be in the deionized water of 30 ~ 50% of described powder mixture quality, after stirring, add in described powder mixture, mediate 2 ~ 4 hours at ambient temperature;
Afterwards, to the mixture after above-mentioned kneading, extruded moulding obtains the carrier of φ 1.5 ~ 2.5mm, length 30 ~ 60mm, under 400 ~ 600 DEG C of temperature conditions, and roasting 4 ~ 8 hours, obtained containing γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3mixing Al 2o 3carrier, and obtain φ 1.5 ~ 2.5mm through shaping screening, column Al that length is 2 ~ 3mm 2o 3carrier.
Certainly, except above-mentioned preparation method, the present invention also comprises the γ type Al obtained by other preparation method 2o 3, ρ type Al 2o 3with α type Al 2o 3mixed carrier.
Wherein also preferably, described 300 ~ 400 object γ type Al 2o 3powder, ρ type Al 2o 3powder and α type Al 2o 3powder obtains by the following method: by 300 ~ 400 order active A l 2o 3powder is calcined 4 ~ 8 hours respectively under 450 ~ 600 DEG C, 800 ~ 900 DEG C, 1100 ~ 1200 DEG C temperature conditions, respectively obtained 300 ~ 400 order γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3powder.
Above support preparation method can obtain the carrier of satisfactory function admirable.
Preferably, described step (1) comprises the following steps:
(1.1) by Al 2o 3carrier impregnation 40 ± 5 DEG C, mass concentration is in the precursor water solution of the base metal active component M of 0.5 ~ 50% 4 ~ 6 hours, solid-liquor separation afterwards, collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~ 600 DEG C of roastings 4 ~ 6 hours, catalyst precursor C1 is obtained; Wherein, in dipping process, the precursor water solution of base metal active component M and carrier A l 2o 3mass ratio be 1:0.8 ~ 1.5;
(1.2) catalyst precursor C1 is immersed in 40 ± 5 DEG C, mass concentration is in the precursor water solution of the noble metal active component ruthenium of 0.5 ~ 3.5% 10 ~ 30 minutes, solid-liquor separation afterwards, collect solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~ 500 DEG C of roastings 4 ~ 6 hours, described catalyst precursor is obtained; Wherein, in dipping process, the precursor water solution of noble metal active component ruthenium and the mass ratio of catalyst precursor C1 are 1:0.5 ~ 1.2.
Each concrete steps and reaction condition can obtain meeting the requirements of catalyst of the present invention above.
In preferred embodiments more of the present invention, in described step (2), employing ruthenium trichloride or nitric acid ruthenium are the presoma of noble metal active component ruthenium, and employing ferric nitrate, copper nitrate, zinc nitrate, ferric trichloride, copper sulphate or zinc sulfate are the presoma of base metal active component M.
The present invention also provide simultaneously and ask to protect adopt said method obtained containing 40 ~ 70% γ type Al 2o 3, 20 ~ 50% ρ type Al 2o 3with 20 ~ 50% α type Al 2o 3described Al 2o 3carrier, described catalyst precursor C1 and described catalyst precursor.
Present invention also offers the application that above-mentioned catalyst absorption essence removes trace sulfide in benzene, its concrete grammar is, under fixed bed reaction condition, at 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, benzene liquid volume air speed 0.5 ~ 4.0h -1under condition, the benzene containing thiophene being the ppm order of magnitude is entered reactor, in outlet benzene, can't detect thiophenes sulfides.Under fixed bed and above-mentioned desulphurization reaction condition, Sulfur capacity >=0.6g (the thiophene)/Kg (catalyst) of prepared catalyst.
Compared with prior art, beneficial effect of the present invention is as follows:
First, the loaded catalyst removing benzene medium sulphide content for essence provided by the invention, can realize the sulfide in benzene to be removed to ppb level, particularly under cryogenic, under fixed bed reaction condition, at 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, benzene liquid volume air speed 0.5 ~ 4.0h -1under condition, the benzene containing thiophene being the ppm order of magnitude is entered the reactor containing this loaded catalyst, thiophenes sulfides is can't detect in outlet benzene, Sulfur capacity>=0.6g (the thiophene)/Kg (catalyst) of the catalyst prepared by the present invention, can successfully by the sulfide in benzene particularly thiophene-based be removed to ppb level, benzene selective hydrogenation technical process can be successfully applied to;
Second, catalyst of the present invention avoids and adopts precious metals pd as main active constituent, can successfully as the replacement scheme of the palladium active constituent catalyst of high cost, ensureing under the prerequisite that catalyst performance is excellent, significantly reduce catalyst manufacturing cost, thus significantly reduce the production cost of benzene selective hydrogenation process;
3rd, catalyst of the present invention has very high selective catalysis adsorption desulfurize performance.Catalyst of the present invention passes through the control of the technical scheme of the preparation of carrier and the selection of two kinds of active constituents and catalyst preparation process condition etc., achieving catalyst activity component of the present invention can effectively with organic sulfur compound effect, and raw material (as benzene) does not affect the object of the effect between sulfide and active constituent;
4th, catalyst of the present invention can not have a negative impact to environment in use procedure, pollution-free;
5th, can regenerate under suitable process conditions after catalyst desulfurizing of the present invention, catalyst can be recycled;
6th; catalyst of the present invention can be widely used in the raw material pretreatment process process that especially benzene selective hydrogenation reacts of benzene hydrogenation field; the serviceability of the catalyst in protection benzene hydrogenation process, thus extend the service life of catalyst in benzene hydrogenation process.
Loaded catalyst of the present invention, thiophene-type sulfide essence particularly close with the boiling point of benzene for the sulfide of trace in benzene can be removed to ppb level, the Sulfur capacity of this loaded catalyst is high, long service life, selective good, pollution-free, the renewable use of catalyst, can be widely used in, in the pretreating process process of benzene hydrogenation, there are good market prospects.
Certainly, implement arbitrary product of the present invention might not need to reach above-described all advantages simultaneously.
Detailed description of the invention
The invention provides a kind of Catalysts and its preparation method and the application that remove trace sulfide in benzene for essence, this catalyst comprises carrier and load active component on the carrier, and described carrier is Al 2o 3carrier, is more preferably containing γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3the Al of mixed-forming 2o 3carrier, the Ru that described active component is 0.5 ~ 5.0% by mass content and the M that mass content is 3.0 ~ 16.0% is formed, and wherein M is one or more in Fe, Cu, Zn.
The above-mentioned preparation method removing the loaded catalyst of trace sulfide in benzene for essence is first prepare Al 2o 3carrier, preferably prepares containing γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3the Al of the function admirable of the mixed-forming of powder 2o 3carrier, adopts program infusion process load base metal and noble metal active component respectively afterwards, then carries out activation process in a mild condition to the catalyst precursor of preparation, obtains the catalyst that described catalytic adsorption essence removes trace sulfide in benzene.
A kind of concrete preparation method's flow process of preferred catalyst of the present invention is as follows:
Al 2o 3support preparation method:
1. by granularity 300 ~ 400 object active A l 2o 3powder is calcined 4 ~ 8 hours respectively under 450 ~ 600 DEG C, 800 ~ 900 DEG C, 1100 ~ 1200 DEG C temperature conditions, obtained 300 ~ 400 order γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3powder;
2. by the γ type Al of some 2o 3powder, ρ type Al 2o 3powder, α type Al 2o 3powder, graphite, sesbania powder mix, wherein γ type Al 2o 3powder 30 ~ 60%, ρ type Al 2o 3powder 20 ~ 50%, α type Al 2o 3powder 20 ~ 50%, graphite 1 ~ 4%, sesbania powder 1 ~ 4%;
3. take the above-mentioned powder mixture prepared of some, take weight be powder mixture quality 1 ~ 4%, mass concentration is the salpeter solution of 45 ~ 63%, takes the deionized water that weight is 30 ~ 50% of powder mixture quality.Salpeter solution is added in deionized water, add in powder mixture after stirring.At ambient temperature, said mixture is mediated 2 ~ 4 hours in kneader;
4. pair above-mentioned kneaded mixture, extruded moulding obtains φ 1.5 ~ 2.5mm, length is the carrier of 30 ~ 60mm, under 450 ~ 600 DEG C of temperature conditions, roasting 4 ~ 8 hours, the obtained Al containing γ type, ρ type and α type 2o 3carrier, and obtain φ 1.5 ~ 2.5mm through shaping screening, column Al that length is 2 ~ 3mm 2o 3carrier.
Active component program dipping method:
1. in 40 ± 5 DEG C of waters bath with thermostatic control, preparation mass concentration is the precursor water solution of the base metal active component M of 0.5 ~ 50%, wherein adopts ferric nitrate, copper nitrate, zinc nitrate, ferric trichloride, copper sulphate or zinc sulfate to be the presoma of base metal active component M; Wherein, in dipping process, the precursor water solution of base metal active component M and carrier A l 2o 3mass ratio be 1:0.8 ~ 1.5;
2. by Al 2o 3carrier impregnation M precursor water solution 4 ~ 6 hours, solid-liquor separation afterwards, collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~ 600 DEG C of roastings 4 ~ 6 hours, obtains catalyst precursor C1;
3., in 40 ± 5 DEG C of waters bath with thermostatic control, preparation mass concentration is the noble metal Ru precursor water solution of 0.5 ~ 20%, and employing ruthenium trichloride or nitric acid ruthenium are the presoma of noble metal active component Ru;
4. catalyst precursor C1 is flooded noble metal salt aqueous solution 10 ~ 30 minutes, solid-liquor separation afterwards, collect solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~ 600 DEG C of roastings 4 ~ 6 hours, obtain catalyst precursor.Wherein, in dipping process, the precursor water solution of noble metal active component ruthenium and the mass ratio of catalyst precursor C1 are 1:0.5 ~ 1.2.
Activating treatment method:
Under fixed bed reaction condition, 200 ~ 450 DEG C, gas volume air speed is 600 ~ 1500h -1, H 2/ N 2volume ratio is under the condition of 0.4 ~ 1.5:1, pressure 0.1 ~ 0.4MPa, carries out pre-activate 2 ~ 6 hours to catalyst precursor, obtains the catalyst that essence of the present invention removes trace sulfide in benzene.
The concrete synthetic method of catalyst of the present invention and step also openly can be changed in conjunction with prior art according to above-mentioned by those skilled in the art, and the specific descriptions in the illustrative description of above-mentioned concrete steps, processing method and parameter and following examples are unintelligible for for limiting protection scope of the present invention.Wherein the working concentration of specific embodiment, temperature, time, pressure and other parameters and concrete application conditions have relation, are not described further herein.
Below in conjunction with specific embodiment, set forth the present invention further.Those skilled in the art the content disclosed by this description can understand and grasp other advantages of the present invention and effect.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.Should be appreciated that, following examples only for further illustrating the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of technical staff and adjustment, still belong to protection scope of the present invention in actual applications.
In addition should be understood that the one or more method steps mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Al 2o 3carrier prepares embodiment
Al 2o 3the preparation of carrier: taking granularity prepared by 450 DEG C of roastings is respectively 300 ~ 400 order γ type Al 2o 3granularity prepared by 14Kg, 850 DEG C of roastings is 300 ~ 400 order ρ type Al 2o 3granularity prepared by 6.0Kg, 1100 DEG C of roastings is 300 ~ 400 order α type Al 2o 39.0Kg, 0.9Kg graphite, 0.6Kg sesbania powder, be uniformly mixed 40min in kneader; Take 0.6Kg 63% salpeter solution and 9.5Kg deionized water respectively, above-mentioned powder mixture is added after salpeter solution and deionized water being mixed, then insert in kneader, after 150min mediated by kneader, extruded moulding obtains φ 2.0mm, length is the column like catalyst carrier of 30 ~ 60mm, under 450 DEG C of temperature conditions, roasting 4 hours, obtained Al 2o 3carrier, obtains φ 2.0mm through shaping screening, column Al that length is 2 ~ 3mm 2o 3carrier, uses in order to catalyst preparing.In addition, in the present embodiment, the diameter of described column like catalyst carrier all can realize object of the present invention at 1.5-2.5mm.Further, those skilled in the art can decide suitable catalyst size according to the size of reactor, above-mentionedly exemplify the number range being not used in and limiting suitable catalyst size.
Embodiment 1
By 26.5g Fe (NO 3) 3.9H 2o is dissolved in 115ml deionized water, is placed in 40 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 150g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 4.7g RuCl 3.nH 2o is dissolved in 110ml deionized water, be placed in 40 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 30min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 400 DEG C, gas is switched to H 2flow is 960ml/min, N 2throughput is 1400ml/min, under pressure is 0.3MPa, temperature 400 DEG C of conditions, keeps 5 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of active component Ru is the content of 1.0%, Fe is 3.0%.
Under fixed bed reaction condition, 140 DEG C, 0.6MPa, will be that the liquid benzene of 0.84ppm squeezes into reactor with the speed of 3.5ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.72g (thiophene)/Kg (catalyst).
Embodiment 2
By 58.5g Fe (NO 3) 3.9H 2o is dissolved in 150ml deionized water, is placed in 40 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 140g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 3.1g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 40 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 300 DEG C, gas is switched to H 2flow is 960ml/min, N 2throughput is 1400ml/min, under pressure is 0.3MPa, temperature 300 DEG C of conditions, keeps 6 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of active component Ru is the content of 0.55%, Fe is 3.9%.
Under fixed bed reaction condition, 140 DEG C, 0.6MPa, will be that the liquid benzene of 0.84ppm squeezes into reactor with the speed of 3.5ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.6g (thiophene)/Kg (catalyst).
Embodiment 3
By 160g Fe (NO 3) 3.9H 2o is dissolved in 150ml deionized water, is placed in 40 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 130g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 25g RuCl 3.nH 2o is dissolved in 120ml deionized water, be placed in 40 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 400 DEG C, gas is switched to H 2flow is 960ml/min, N 2throughput is 1400ml/min, under pressure is 0.3MPa, temperature 400 DEG C of conditions, keeps 3 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of active component Ru is the content of 4.75%, Fe is 14.6%.
Under fixed bed reaction condition, 140 DEG C, 0.6MPa, will be that the liquid benzene of 0.84ppm squeezes into reactor with the speed of 3.5ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.8g (thiophene)/Kg (catalyst).
Embodiment 4
By 32.5g Cu (NO 3) 2.3H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, the Al prepared by 150g 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 480 DEG C of temperature conditions, obtains catalyst precursor C1.
By 4.0g RuCl 3.nH 2o is dissolved in 120ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 15min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 380 DEG C, gas is switched to H 2flow is 1050ml/min, N 2throughput is 1000ml/min, under pressure is 0.2MPa, temperature 380 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of active component Ru is the content of 0.65%, Cu is 3.81%.
Under fixed bed reaction condition, 155 DEG C, 0.9MPa, will be that the liquid benzene of 0.87ppm squeezes into reactor with the speed of 3.2ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.65g (thiophene)/Kg (catalyst).
Embodiment 5
By 35.0g Cu (NO 3) 2.3H 2o is dissolved in 140ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, the Al prepared by 140g 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 480 DEG C of temperature conditions, obtains catalyst precursor C1.
By 3.15g RuCl 3.nH 2o is dissolved in 120ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 15min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 380 DEG C, gas is switched to H 2flow is 1050ml/min, N 2throughput is 1000ml/min, under pressure is 0.2MPa, temperature 380 DEG C of conditions, keeps 5 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of active component Ru is the content of 0.5%, Cu is 3.0%.
Under fixed bed reaction condition, 155 DEG C, 0.9MPa, will be that the liquid benzene of 0.87ppm squeezes into reactor with the speed of 3.2ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.63g (thiophene)/Kg (catalyst).
Embodiment 6
By 62.0g Cu (NO 3) 2.3H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, the Al prepared by 120g 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 480 DEG C of temperature conditions, obtains catalyst precursor C1.
By 37.0g RuCl 3.nH 2o is dissolved in 120ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 30min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 350 DEG C, gas is switched to H 2flow is 1050ml/min, N 2throughput is 1000ml/min, under pressure is 0.2MPa, temperature 350 DEG C of conditions, keeps 6 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of active component Ru is the content of 4.8%, Cu is 14.9%.
Under fixed bed reaction condition, 155 DEG C, 0.9MPa, will be that the liquid benzene of 0.87ppm squeezes into reactor with the speed of 3.2ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.80g (thiophene)/Kg (catalyst).
Embodiment 7
By 40g Zn (NO 3) 2.6H 2o is dissolved in 150ml deionized water, is placed in 40 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 150g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 15 hours under 120 DEG C of conditions, and then roasting 4 hours under 400 DEG C of temperature conditions, obtains catalyst precursor C1.
By 3.8g RuCl 3.nH 2o is dissolved in 110ml deionized water, be placed in 40 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 15min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 240 DEG C, gas is switched to H 2flow is 980ml/min, N 2throughput is 1100ml/min, under pressure is 0.4MPa, temperature 240 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes benzene medium sulphide content.In this catalyst prod, the content of active component Ru is the content of 0.7%, Zn is 3.3%.
Under fixed bed reaction condition, 160 DEG C, 1.1MPa, will be that the liquid benzene of 0.75ppm squeezes into reactor with the speed of 3.6ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.63g (thiophene)/Kg (catalyst).
Embodiment 8
By 38.5g Zn (NO 3) 2.6H 2o is dissolved in 150ml deionized water, is placed in 40 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 140g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 15 hours under 120 DEG C of conditions, and then roasting 4 hours under 400 DEG C of temperature conditions, obtains catalyst precursor C1.
By 3.5g RuCl 3.nH 2o is dissolved in 110ml deionized water, be placed in 40 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 450 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 240 DEG C, gas is switched to H 2flow is 980ml/min, N 2throughput is 1100ml/min, under pressure is 0.4MPa, temperature 240 DEG C of conditions, keeps 6 hours, obtains the catalyst that essence removes benzene medium sulphide content.In this catalyst prod, the content of active component Ru is the content of 0.5%, Zn is 3.0%.
Under fixed bed reaction condition, 160 DEG C, 1.1MPa, will be that the liquid benzene of 0.75ppm squeezes into reactor with the speed of 3.6ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.6g (thiophene)/Kg (catalyst).
Embodiment 9
By 225g Zn (NO 3) 2.6H 2o is dissolved in 150ml deionized water, is placed in 40 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 150g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 15 hours under 120 DEG C of conditions, and then roasting 6 hours under 400 DEG C of temperature conditions, obtains catalyst precursor C1.
By 35g RuCl 3.nH 2o is dissolved in 110ml deionized water, be placed in 40 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 240 DEG C, gas is switched to H 2flow is 980ml/min, N 2throughput is 1100ml/min, under pressure is 0.4MPa, temperature 240 DEG C of conditions, keeps 6 hours, obtains the catalyst that essence removes benzene medium sulphide content.In this catalyst prod, the content of active component Ru is the content of 4.3%, Zn is 13.8%.
Under fixed bed reaction condition, 160 DEG C, 1.1MPa, will be that the liquid benzene of 0.75ppm squeezes into reactor with the speed of 3.6ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.8g (thiophene)/Kg (catalyst).
Embodiment 10
By 27.5g Fe (NO 3) 3.9H 2o, 18.0g Cu (NO 3) 2.3H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 150g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 5.2g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 10min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 400 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 400 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 0.65%, Fe be 2.0%, Cu is 1.5%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.65g (thiophene)/Kg (catalyst).
Embodiment 11
By 28.0g Fe (NO 3) 3.9H 2o, 19.5g Cu (NO 3) 2.3H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 120g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 3 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 4.8g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 350 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 450 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 450 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 0.5%, Fe be 1.6%, Cu is the content sum of 1.5%, Fe and Cu is 3.1%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.63g (thiophene)/Kg (catalyst).
Embodiment 12
By 77.0g Fe (NO 3) 3.9H 2o, 73.0g Cu (NO 3) 2.3H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 140g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 5 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 29.5g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 400 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 400 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 4.2%, Fe be 6.1%, Cu is the content sum of 7.0%, Fe and Cu is 13.1%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.77g (thiophene)/Kg (catalyst).
Embodiment 13
By 21.0g Fe (NO 3) 3.9H 2o, 24.0g Zn (NO 3) 2.6H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 120g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 4.1g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 350 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 450 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 450 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 0.54%, Fe be 1.7%, Zn is the content sum of 1.9%, Fe and Zn is 3.6%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.6g (thiophene)/Kg (catalyst).
Embodiment 14
By 101.0g Fe (NO 3) 3.9H 2o, 108.0g Zn (NO 3) 2.6H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 120g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 36.5g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 3 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 400 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 400 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 4.3%, Fe be 7.2%, Zn is the content sum of 7.5%, Fe and Zn is 14.7%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.75g (thiophene)/Kg (catalyst).
Embodiment 15
By 13.9g Cu (NO 3) 2.3H 2o, 22.4g Zn (NO 3) 2.6H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 120g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 2 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 4.2g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 380 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 380 DEG C of conditions, keeps 6 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 0.58%, Cu be 1.4%, Zn is the content sum of 1.8%, Cu and Zn is 3.2%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.62g (thiophene)/Kg (catalyst).
Embodiment 16
By 84.5g Cu (NO 3) 2.3H 2o, 109.5g Zn (NO 3) 2.6H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 130g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 34.0g RuCl 3.nH 2o is dissolved in 125ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 30min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 400 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 400 DEG C of conditions, keeps 6 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 4.1%, Cu be 6.9%, Zn is the content sum of 7.5%, Cu and Zn is 14.4%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.76g (thiophene)/Kg (catalyst).
Embodiment 17
By 68.0g Cu (NO 3) 2.3H 2o, 96.0g Zn (NO 3) 2.6H 2o, 110.0g Fe (NO 3) 3.9H 2o is dissolved in 150ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 150g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 6 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 5 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 36.5g RuCl 3.nH 2o is dissolved in 140ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 30min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 450 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 450 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 4.7%, Cu be 4.6%, Zn is that the content of 4.5%, Fe is 5.8%, Cu, the content sum of Zn and Fe is 14.9%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.77g (thiophene)/Kg (catalyst).
Embodiment 18
By 17.8g Cu (NO 3) 2.3H 2o, 18.5g Zn (NO 3) 2.6H 2o, 56.5g Fe (NO 3) 3.9H 2o is dissolved in 130ml deionized water, is placed in 45 DEG C of waters bath with thermostatic control, by the Al of above-mentioned for 130g preparation 2o 3carrier puts into the solution of above-mentioned preparation, floods after 3 hours, filter and collect solid phase under stirring condition, drying 12 hours under 120 DEG C of conditions, and then roasting 4 hours under 450 DEG C of temperature conditions, obtains catalyst precursor C1.
By 4.5g RuCl 3.nH 2o is dissolved in 130ml deionized water, be placed in 45 DEG C of waters bath with thermostatic control, catalyst precursor C1 is put into the ruthenium trichloride aqueous solution of preparation, 20min is flooded under stirring condition, filter and collect solid phase, under 120 DEG C of conditions dry 12 hours, then roasting 4 hours under 380 DEG C of temperature conditions, obtained catalyst precursor C2.
140ml catalyst precursor is loaded in the fixed bed reactors of φ 17 × 1800, adopt N 2purge, when temperature rises to 450 DEG C, gas is switched to H 2flow is 1000ml/min, N 2throughput is 1200ml/min, under pressure is 0.4MPa, temperature 450 DEG C of conditions, keeps 4 hours, obtains the catalyst that essence removes trace sulfide in benzene.In this catalyst prod, the content of the content of active component Ru to be the content of 0.53%, Cu be 1.65%, Zn is that the content of 1.38%, Fe is 4.6%, Cu, the content sum of Zn and Fe is 7.63%.
Under fixed bed reaction condition, 150 DEG C, 0.7MPa, will be that the liquid benzene of 0.92ppm squeezes into reactor with the speed of 4.0ml/min containing thiophene, under experimental conditions, adopt gas chromatographicanalyzer to can't detect outlet benzene and contain any thiophene-type sulfide, under experimental conditions, the Sulfur capacity recording catalyst is 0.65g (thiophene)/Kg (catalyst).
The catalytic adsorption desulphurization catalyst that the above embodiment of the present invention provides, there is very high activity under experimental conditions, effectively essence can remove the sulfide of trace in benzene, this catalyst can make the content of benzene raw materials medium sulphide content be reduced to ppb level by ppm level, can be applicable to, in the raw material pretreatment process process of benzene selective hydrogenation reaction, effectively to extend the service life of catalyst in benzene hydrogenation process.
In use in current suitability for industrialized production is all adopt the palladium catalyst adopted from external imported technology to remove thiophene-type sulfide micro-in benzene for essence, because precious metal palladium is expensive, price is 8 ~ 10 times of ruthenium, and therefore developing alternative fine desulfurization catalyst becomes the bottleneck reducing enterprise's production cost.
The present inventor combines achievement in research in the past in this field and on a large amount of experimental study bases, find that ruthenium load has desulfurization performance more better than palladium on suitable carrier, room pilot scale and the experiment of industrial side line, show the palladium catalyst adopted in the complete alternative former patented technology of load ruthenium catalyst of the present invention by experiment.
Useful achievement major embodiment of the present invention: (a) adopts catalyst of the present invention will greatly to reduce the production cost of enterprise, significantly improves the economic benefit of enterprise; B () catalyst of the present invention is the thiophene-type sulfide proposing first to remove for essence in benzene, due to the boiling point of the thiophene-type sulfide in benzene and benzene close, therefore remove more difficult.
Under the instruction of the present invention and above-described embodiment, those skilled in the art are easy to predict, each raw material cited by the present invention and method can realize the present invention, and the bound value of each raw material and technique, interval value can realize the present invention, do not enumerate embodiment at this.

Claims (13)

1. essence removes a catalyst for trace sulfide in benzene, and comprise carrier and load active component on the carrier, it is characterized in that, described carrier is Al 2o 3carrier, described active component accounts for by mass content the base metal active component M that the noble metal active component ruthenium of whole catalyst quality 0.5 ~ 5.0% and mass content account for whole catalyst quality 3.0 ~ 16.0% and forms, and wherein M is one or more in Fe, Cu, Zn.
2. essence as claimed in claim 1 removes the catalyst of trace sulfide in benzene, it is characterized in that, described carrier is for containing 40 ~ 70% γ type Al 2o 3, 20 ~ 50% ρ type Al 2o 3with 20 ~ 50% α type Al 2o 3mixing Al 2o 3carrier.
3. essence as claimed in claim 2 removes the catalyst of trace sulfide in benzene, it is characterized in that, described carrier is φ 1.5 ~ 2.5mm, cylindrical particle that length is 2 ~ 3mm.
4. the essence according to any one of claim 1-3 removes the catalyst of trace sulfide in benzene, it is characterized in that, under fixed bed reaction condition, at 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, benzene liquid volume air speed 0.5 ~ 4.0h -1, benzene feed is under the condition of the ppm order of magnitude containing thiophene, the Sulfur capacity>=0.6g thiophene/Kg catalyst of described catalyst.
5. the essence according to any one of claim 1-4 removes a preparation method for the catalyst of trace sulfide in benzene, it is characterized in that, comprises the following steps:
(1) adopt program infusion process successively at described Al 2o 3the presoma of supported on carriers base metal active constituent M and noble metal active component Ru, obtains catalyst precursor;
(2) under fixed bed reaction condition, 200 ~ 450 DEG C, gas volume air speed is 600 ~ 1500h -1, H 2/ N 2volume ratio is under the condition of 0.4 ~ 1.5:1, pressure 0.1 ~ 0.4MPa, carries out pre-activate 2 ~ 6 hours to described catalyst precursor, obtains the catalyst that described essence removes trace sulfide in benzene.
6. essence as claimed in claim 5 removes the preparation method of the catalyst of trace sulfide in benzene, it is characterized in that, also comprises: prepared described Al by the following method before described step (1) 2o 3carrier:
First, by graphite, sesbania powder, 300 ~ 400 object γ type Al 2o 3powder, ρ type Al 2o 3powder and α type Al 2o 3powder mixes and obtains powder mixture, wherein γ type Al 2o 3powder 40 ~ 70%, ρ type Al 2o 3powder 20 ~ 50%, α type Al 2o 3powder 20 ~ 50%, graphite 1 ~ 4%, sesbania powder 1 ~ 4%;
Then, be 1 ~ 4% of described powder mixture quality by quality, concentration be 45 ~ 63% salpeter solution to add quality be in the deionized water of 30 ~ 50% of described powder mixture quality, after stirring, add in described powder mixture, mediate 2 ~ 4 hours at ambient temperature;
Afterwards, to the mixture after above-mentioned kneading, extruded moulding obtains the carrier of φ 1.5 ~ 2.5mm, length 30 ~ 60mm, under 400 ~ 600 DEG C of temperature conditions, and roasting 4 ~ 8 hours, obtained containing γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3mixing Al 2o 3carrier, and obtain φ 1.5 ~ 2.5mm through shaping screening, column Al that length is 2 ~ 3mm 2o 3carrier.
7. essence as claimed in claim 6 removes the preparation method of the catalyst of trace sulfide in benzene, it is characterized in that, described 300 ~ 400 object γ type Al 2o 3powder, ρ type Al 2o 3powder and α type Al 2o 3powder obtains by the following method: by 300 ~ 400 order active A l 2o 3powder is calcined 4 ~ 8 hours respectively under 450 ~ 600 DEG C, 800 ~ 900 DEG C, 1100 ~ 1200 DEG C temperature conditions, respectively obtained 300 ~ 400 order γ type Al 2o 3, ρ type Al 2o 3with α type Al 2o 3powder.
8. essence as claimed in claim 5 removes the preparation method of the catalyst of trace sulfide in benzene, and it is characterized in that, described step (1) comprises the following steps:
(1.1) by described Al 2o 3carrier impregnation 40 ± 5 DEG C, mass concentration is in the precursor water solution of the base metal active component M of 0.5 ~ 50% 2 ~ 6 hours, solid-liquor separation afterwards, collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~ 600 DEG C of roastings 4 ~ 6 hours, catalyst precursor C1 is obtained; Wherein, in dipping process, the precursor water solution of base metal active component M and carrier A l 2o 3mass ratio be 1:0.8 ~ 1.5;
(1.2) catalyst precursor C1 is immersed in 40 ± 5 DEG C, mass concentration is in the precursor water solution of the noble metal active component ruthenium of 0.5 ~ 3.5% 10 ~ 30 minutes, solid-liquor separation afterwards, collect solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 300 ~ 600 DEG C of roastings 4 ~ 6 hours, catalyst precursor is obtained; Wherein, in dipping process, the precursor water solution of noble metal active component ruthenium and the mass ratio of catalyst precursor C1 are 1:0.5 ~ 1.2.
9. the essence as described in claim 5 or 8 removes the preparation method of the catalyst of trace sulfide in benzene, it is characterized in that, in described step (1), employing ruthenium trichloride or nitric acid ruthenium are the presoma of noble metal active component ruthenium, and employing ferric nitrate, copper nitrate, zinc nitrate, ferric trichloride, copper sulphate or zinc sulfate are the presoma of base metal active component M.
10. the essence according to any one of a claim 6-7 remove that the preparation method of the catalyst of trace sulfide in benzene obtains containing 40 ~ 70% γ type Al 2o 3, 20 ~ 50% ρ type Al 2o 3with 20 ~ 50% α type Al 2o 3described Al 2o 3carrier.
The described catalyst precursor C1 that the preparation method that essence according to any one of 11. 1 kinds of claim 5-9 removes the catalyst of trace sulfide in benzene obtains.
The described catalyst precursor that the preparation method that essence according to any one of 12. 1 kinds of claim 5-9 removes the catalyst of trace sulfide in benzene obtains.
Essence according to any one of 13. 1 kinds of claim 1-4 removes the application of the catalyst of trace sulfide in benzene, it is characterized in that, under fixed bed reaction condition, at 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, benzene liquid volume air speed 0.5 ~ 4.0h -1under condition, the benzene being the ppm order of magnitude is entered reactor, in the benzene in exit, can't detect thiophenes sulfides containing thiophene.
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