CN104998657B - Catalyst of trace sulfide and its preparation method and application in essence removing benzene - Google Patents
Catalyst of trace sulfide and its preparation method and application in essence removing benzene Download PDFInfo
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- CN104998657B CN104998657B CN201510367391.5A CN201510367391A CN104998657B CN 104998657 B CN104998657 B CN 104998657B CN 201510367391 A CN201510367391 A CN 201510367391A CN 104998657 B CN104998657 B CN 104998657B
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Abstract
The invention discloses catalyst of trace sulfide in a kind of essence removing benzene and its preparation method and application, the formula of the catalyst is Ru M/Al2O3, its preparation method is with Al2O3For carrier, the active component for using program infusion process load quality content to be made up of 0.5~5.0% Ru and the M of mass content 3.0~16.0%, wherein M is the one or more in Fe, Cu, Zn.Catalyst prepared by the present invention can be used for trace sulfide such as thiophene-type sulfide in essence removing benzene.The loaded catalyst of the present invention, avoid and use precious metal palladium, thus cost is low, and thiophene-type sulfide essence micro in benzene can be removed to ppb levels, the Sulfur capacity of catalyst is high, service life is long, selectivity is good, pollution-free, the renewable use of catalyst, can be widely applied to during the pretreating process of benzene hydrogenation.
Description
Technical field
The invention belongs to environmental protection and chemical technology field, is related to the catalyst that a kind of essence removes trace sulfide in benzene
And its preparation method and application, relate generally in a kind of essence removing benzene the loaded catalyst of micro thiophene-type sulfide and its
Preparation method and application.
Background technology
Cyclohexene is a kind of important organic synthesis intermediate, and it is current directly to prepare cyclohexene using benzene selective hydrogenation
Economically most viable technology path.Because benzene hydrogenation process generally uses noble metal catalyst, micro sulfide in benzene
Noble metal catalyst slow poisoning can be caused, so that the conversion ratio of benzene selective hydrogenation course of reaction and selectivity are gradually reduced,
Until catalyst complete deactivation, and the activity and selectivity of regenerated catalyst can not return to the primality of fresh catalyst
Energy.To extend the service life of catalyst, course of reaction need to be raw material with the benzene of high-purity, and wherein sulfur content requirement is reduced to
Ppb levels.
Petrobenzene is to refine oil the accessory substance in process catalytic reforming reaction, because of the thiophenes and benzene of petrobenzene
Boiling point approach, be difficult to conventional distillation method its is completely separable, therefore petrobenzene more or less contains a number of sulphur
Compound, traditional hydrodesulfurizationprocess process use such as aluminum oxide as carrier, and load W, Ni, Mo etc. are the catalyst of active constituent,
Under conditions of higher hydrogen oil ratio and reaction temperature, the organic sulfur compound in benzene is changed into inorganic sulphide, due to the reaction
Process is limited by thermodynamically, it is difficult to which total sulfur content in benzene feedstock is down into ppb levels.In addition, the side as used azeotropic distillation
Method, it can realize separate thiophenes with benzene in theory, not only can obtain purified petroleum benzin but also can obtain thiophenes, but should
In the case that sulfide content that method is only applicable in benzene is higher, and for the benzene feedstock that total sulfur content is ppm levels, using altogether
The method for boiling rectifying separates sulfide therein, is all economically and technically infeasible.With above-mentioned and other de-
Sulphur method is compared, and catalytic adsorption method is the method for being the most suitably used to remove trace sulfide in benzene, realizes this process
Key is to use efficient catalytic adsorption desulphurization catalyst.
CN101612549A discloses one kind with γ-Al2O3For carrier, Ag2O and CeO2For the catalyst of active constituent, use
In removing thiophene and CS in coking benzene2.Under normal pressure, room temperature condition, the thiophene in coking benzene can be removed to from 500ppm
Below 20ppm, while can be by the CS in coking benzene2Below 1ppm is removed to from 200ppm, it can be difficult to realizing the sulphur in benzene
Compound is removed to ppb levels.
CN103480325A discloses one kind and dissolves palladium in organic solvent, is used to take off using prepared by infusion process
Except the Pd/Al of sulfide in benzene2O3Desulphurization catalyst, the sulfide in refining benzene can be down to ppb levels from ppm levels under experiment condition.
The catalyst of sulfide in the above-mentioned published removing benzene for catalytic adsorption, otherwise it is to be difficult under cryogenic
Realize and the sulfide in benzene is removed to ppb levels, thus benzene selective hydrogenation technical process can not be applied to；It is that your gold used
Belong to Pd as main active constituent, because precious metal palladium is expensive, the production cost of benzene selective hydrogenation process will be dramatically increased.And
At present, performance is not yet disclosed in the prior art quite or preferably to can be used for substituting using precious metals pd as main active constituent
The loaded catalyst of catalyst.
The content of the invention
The present invention provides a kind of catalyst of trace sulfide in essence removing benzene, and the catalyst is loaded catalyst, this
Invention also provides the preparation method of the loaded catalyst and its vulcanized for removing sulfide particularly thiophene-based in benzene simultaneously
The purposes of thing.
The loaded catalyst of the present invention is by using γ types Al2O3, ρ types Al2O3With α types Al2O3It is prepared by powder mixed-forming
Go out the Al of function admirable2O3Carrier, and base metal and the desulphurizing activated component of noble metal are loaded using program infusion process respectively, it is right
The catalyst precursor of preparation carries out prereduction, is prepared for a kind of catalysis that trace sulfide in benzene is removed in a manner of catalytic adsorption
Agent, the catalyst have very high selective catalysis absorption desulfurization performance, can realize sulfide micro in benzene from ppm levels
It is reduced to ppb levels.Catalyst of the present invention can be widely applied to the raw material pretreatment process mistake of benzene hydrogenation especially benzene selective hydrogenation
Cheng Zhong, the performance of benzene hydrogenating catalyst is protected, so as to extend the service life of catalyst during benzene hydrogenation.
The catalyst of trace sulfide in a kind of essence removing benzene provided by the invention, its formula is Ru-M/Al2O3, this is urged
Agent includes the active component of carrier and load on the carrier, and the carrier is Al2O3Carrier, the active component is by expensive
Metal active constituent Ru and base metal active component M are formed, and wherein M is the one or more in Fe, Cu, Zn, described expensive
The mass content of metal active constituent ruthenium accounts for whole catalyst quality 0.5~5.0%, the matter of the base metal active component M
Amount content accounts for whole catalyst quality 3.0~16.0%.
The catalyst of trace sulfide in above-mentioned essence removing benzene provided by the invention, with noble metal active component Ru and non-expensive
Metal active constituent M, so as to instead of costly palladium, reduces the raw material of catalyst collectively as catalyst activity component
Cost.Also, due to the synergy between active constituent the catalytic activity of catalyst is influenceed it is very big, therefore only according to
The above-mentioned technical proposal of the present invention selects suitable active constituent and suitable proportioning, and the collaboration of each active constituent of competence exertion is made
With so as to ensure catalytic performance that catalyst has had.
The present invention essence removing benzene in trace sulfide catalyst under the conditions of fixed bed reaction, 120~180 DEG C,
0.4~1.5MPa, 0.5~4.0h of benzene liquid volume air speed-1, benzene feed is the catalysis under conditions of the ppm orders of magnitude containing thiophene
The Sulfur capacity of agent >=0.6g thiophene/Kg catalyst.
Conventional Al can be selected in the catalyst carrier of the present invention2O3Carrier, but in a preferred embodiment of the invention, it is described
Carrier is to contain γ types Al2O3, ρ types Al2O3With α types Al2O3Mixing Al2O3Carrier.Further preferably, contain in the carrier
40~70% γ types Al2O3, 20~50% ρ types Al2O3With 20~50% α types Al2O3, the carrier specification be φ 1.5~
2.5mm, a length of 2~3mm cylindrical particle.During due to removing the thiophene-type sulfide in benzene using chemiadsorption, catalyst
Surface acidic-basic property it is very big to the performance impact of catalyst, catalyst of the invention uses γ types Al2O3, ρ types Al2O3With α types
Al2O3Mixed-forming prepares alumina carrier to powder by a certain percentage, can effectively adjust preparation-obtained catalyst table
The acid-base property in face, so as to prepare the catalyst of micro thiophene-type sulfide in the catalytic adsorption of more excellent performance essence removing benzene.
Meanwhile the present invention uses γ types Al2O3, ρ types Al2O3With α types Al2O3Mixed-forming prepares three required oxygen to powder by a certain percentage
Change two alumina supporters, can also be prepared according to the content for being actually needed the alumina powder for adjusting variant crystal formation various different strong
The catalyst of degree, better meet the demand of differential responses process.
It is including following present invention also offers a kind of preparation method of the catalyst of trace sulfide in above-mentioned essence removing benzene
Step：
(1) using program infusion process successively in the Al2O3Supported on carriers base metal active constituent M and noble metal are lived
Property component Ru presoma, obtains catalyst precursor；
(2) it is 600~1500h in 200~450 DEG C, gas volume air speed after under the conditions of fixed bed reaction-1、H2/
N2Volume ratio is 0.4~1.5:1st, under conditions of 0.1~0.4MPa of pressure, pre-activate 2~6 is carried out to the catalyst precursor
Hour, obtain the catalyst of trace sulfide in the essence removing benzene.
Preferably, also include before the step (1)：It is prepared by the following method the Al2O3Carrier：
First, by graphite, sesbania powder, 300~400 mesh γ types Al2O3Powder, ρ types Al2O3Powder and α types Al2O3Powder mixing is equal
It is even to obtain powder mixture, wherein γ types Al2O3Powder 40~70%, ρ types Al2O3Powder 20~50%, α types Al2O3Powder 20~50%,
Graphite 1~4%, sesbania powder 1~4%；
Then, the salpeter solution that quality is the powder mixture quality 1~4%, concentration is 45~63% is added
Quality is in 30~50% deionized water of the powder mixture quality, after stirring, adds the powder mixture
In, mediate 2~4 hours at ambient temperature；
Afterwards, to the mixture after above-mentioned kneading, extruded moulding obtains 1.5~2.5mm of φ, 30~60mm of length load
Body, under 400~600 DEG C of temperature conditionss, it is calcined 4~8 hours, is made and contains γ types Al2O3, ρ types Al2O3With α types Al2O3It is mixed
Close Al2O3Carrier, and shaped screening obtains 1.5~2.5mm of φ, a length of 2~3mm column Al2O3Carrier.
Certainly, in addition to above-mentioned preparation method, the present invention also includes the γ types Al obtained by other preparation methods2O3, ρ types
Al2O3With α types Al2O3Mixed carrier.
Wherein it is also preferred that the γ types Al of 300~400 mesh2O3Powder, ρ types Al2O3Powder and α types Al2O3Powder passes through with lower section
Method is made：By 300~400 mesh activity Al2O3Powder is respectively in 450~600 DEG C, 800~900 DEG C, 1100~1200 DEG C of temperature conditionss
Lower calcining 4~8 hours, is made 300~400 mesh γ types Al respectively2O3, ρ types Al2O3With α types Al2O3Powder.
Above support preparation method can obtain the carrier of satisfactory function admirable.
Preferably, the step (1) comprises the following steps：
(1.1) by Al2O3Carrier impregnation is 0.5~50% base metal active component M's in 40 ± 5 DEG C, mass concentration
4~6 hours in precursor water solution, solid-liquor separation afterwards collects solid phase, 110~140 DEG C of dryings 10~18 hours, Ran Hou
400~600 DEG C are calcined 4~6 hours, obtain catalyst precursor C1；Wherein, in dipping process, base metal active component M's
Precursor water solution and carrier Al2O3Mass ratio be 1：0.8~1.5；
(1.2) by catalyst precursor C1 be immersed in 40 ± 5 DEG C, mass concentration be 0.5~3.5% noble metal active group
Divide in the precursor water solution of ruthenium 10~30 minutes, solid-liquor separation, collects solid phase afterwards, and 110~140 DEG C of dryings 10~18 are small
When, then it is calcined 4~6 hours at 400~500 DEG C, obtains the catalyst precursor；Wherein, in dipping process, noble metal is lived
Property component ruthenium precursor water solution and catalyst precursor C1 mass ratio be 1：0.5~1.2.
Each specific steps and reaction condition can obtain the catalyst of the invention for reaching requirement above.
In some preferred embodiments of the present invention, in the step (2), ruthenium trichloride or nitric acid ruthenium are used as your gold
Belong to the presoma of active component ruthenium, use ferric nitrate, copper nitrate, zinc nitrate, ferric trichloride, copper sulphate or zinc sulfate as your non-gold
Belong to active component M presoma.
The present invention is also provided and is claimed using containing 40~70% γ types Al made from the above method simultaneously2O3, 20~
50% ρ types Al2O3With 20~50% α types Al2O3The Al2O3Before carrier, the catalyst precursor C1 and the catalyst
Drive body.
Present invention also offers the application that above-mentioned catalyst adsorbs trace sulfide in essence removing benzene, its specific method
For, under the conditions of fixed bed reaction, 120~180 DEG C, 0.4~1.5MPa, 0.5~4.0h of benzene liquid volume air speed-1Condition
Under, reactor will be entered for the benzene of the ppm orders of magnitude containing thiophene, export in benzene and can't detect thiophenes sulfides.In fixed bed and upper
Under the conditions of stating desulphurization reaction, Sulfur capacity >=0.6g (thiophene)/Kg (catalyst) of prepared catalyst.
Compared with prior art, beneficial effects of the present invention are as follows：
First, the loaded catalyst of sulfide in benzene is removed provided by the present invention for essence, can be real under cryogenic
The sulfide in benzene is now removed to ppb levels, specifically, under the conditions of fixed bed reaction, 120~180 DEG C, 0.4~
1.5MPa, 0.5~4.0h of benzene liquid volume air speed-1Under the conditions of, urged entering containing thiophene for the benzene of the ppm orders of magnitude containing the support type
The reactor of agent, export and thiophenes sulfides are can't detect in benzene, Sulfur capacity >=0.6g (thiophenes of the catalyst prepared by the present invention
Fen)/Kg (catalyst), the particularly thiophene-based of the sulfide in benzene successfully can be removed to ppb levels, can be successfully applied to
Benzene selective hydrogenation technical process；
Second, catalyst of the invention is avoided using precious metals pd as main active constituent, can be successfully as height
The alternative solution of the palladium active constituent catalyst of cost, on the premise of ensureing that catalyst performance is excellent, significantly reduce catalysis
Agent manufacturing cost, so as to significantly reduce the production cost of benzene selective hydrogenation process；
3rd, catalyst of the present invention has very high selective catalysis absorption desulfurization performance.Catalyst of the present invention passes through
The preparation of carrier and the control of the technical scheme of the selection of two kinds of active constituents and catalyst preparation process condition etc., are realized
Catalyst activity component of the present invention can be acted on effectively with organic sulfur compound, and raw material (such as benzene) does not influence sulfide and active constituent
Between effect purpose；
4th, catalyst of the present invention will not be had a negative impact using process to environment, pollution-free；
5th, it can be regenerated under suitable process conditions after catalyst desulfurizing of the present invention, catalyst is recyclable to be made
With；
6th, the raw material that catalyst of the present invention can be widely applied to the especially benzene selective hydrogenation reaction of benzene hydrogenation field is located in advance
During science and engineering skill, the performance of the catalyst during protection benzene hydrogenation, so as to extend during benzene hydrogenation
The service life of catalyst.
The loaded catalyst of the present invention, sulfide micro in benzene can be particularly to the thiophene-based close with the boiling point of benzene
Sulfide essence is removed to ppb levels, and the Sulfur capacity height of the loaded catalyst, service life is long, selectivity is good, pollution-free, catalyst
It renewable use, can be widely applied to during the pretreating process of benzene hydrogenation, there are good market prospects.
Certainly, any product for implementing the present invention it is not absolutely required to reach all the above advantage simultaneously.
Embodiment
It is used for catalyst of trace sulfide and its preparation method and application in essence removing benzene the invention provides a kind of, should
Catalyst includes the active component of carrier and load on the carrier, and the carrier is Al2O3Carrier, more preferably contain γ
Type Al2O3, ρ types Al2O3With α types Al2O3Mixed-forming Al2O3Carrier, the active component by mass content be 0.5~
5.0% Ru and mass content is made up of 3.0~16.0% M, and wherein M is the one or more in Fe, Cu, Zn.
The above-mentioned preparation method for being used for the loaded catalyst of trace sulfide in essence removing benzene is to prepare Al first2O3
Carrier, preferably prepare containing γ types Al2O3, ρ types Al2O3With α types Al2O3The Al of the function admirable of the mixed-forming of powder2O3Carry
Body, base metal and noble metal active component are loaded using program infusion process respectively afterwards, then to the complex catalyst precursor of preparation
Body carries out activation process in a mild condition, obtains the catalyst of trace sulfide in described catalytic adsorption essence removing benzene.
A kind of specific preparation method flow of preferable catalyst of the present invention is as follows：
Al2O3Support preparation method：
1. by the active Al of the mesh of granularity 300~4002O3Powder respectively 450~600 DEG C, 800~900 DEG C, 1100~1200
Calcined 4~8 hours under DEG C temperature conditionss, 300~400 mesh γ types Al are made2O3, ρ types Al2O3With α types Al2O3Powder；
2. by a number of γ types Al2O3Powder, ρ types Al2O3Powder, α types Al2O3Powder, graphite, sesbania powder are well mixed, its
Middle γ types Al2O3Powder 30~60%, ρ types Al2O3Powder 20~50%, α types Al2O3Powder 20~50%, graphite 1~4%, sesbania powder 1
~4%；
3. weigh the above-mentioned powder mixture prepared of certain amount, weigh that weight is powder mixture quality 1~
4%th, mass concentration is 45~63% salpeter solution, weighs 30~50% deionization that weight is powder mixture quality
Water.Salpeter solution is added in deionized water, is stirring evenly and then adding into powder mixture.At ambient temperature, will be above-mentioned mixed
Compound is mediated 2~4 hours in kneader；
4. pair above-mentioned kneaded mixture, the carrier that extruded moulding obtains 1.5~2.5mm of φ, length is 30~60mm,
Under 450~600 DEG C of temperature conditionss, it is calcined 4~8 hours, the Al containing γ types, ρ types and α types is made2O3Carrier, and it is shaped
Screening obtains 1.5~2.5mm of φ, a length of 2~3mm column Al2O3Carrier.
Active component program dipping method：
1. in 40 ± 5 DEG C of waters bath with thermostatic control, before preparing the base metal active component M that mass concentration is 0.5~50%
The body aqueous solution is driven, wherein using ferric nitrate, copper nitrate, zinc nitrate, ferric trichloride, copper sulphate or zinc sulfate as base metal activity
Component M presoma；Wherein, in dipping process, base metal active component M precursor water solution and carrier Al2O3Quality
Than for 1：0.8~1.5；
2. by Al2O3Carrier impregnation M precursor water solutions 4~6 hours, afterwards solid-liquor separation collect solid phase, and 110~140
DEG C dry 10~18 hours, be then calcined 4~6 hours at 400~600 DEG C, obtain catalyst precursor C1；
3. in 40 ± 5 DEG C of waters bath with thermostatic control, the noble metal Ru precursor water solutions that mass concentration is 0.5~20% are prepared,
Use the presoma of ruthenium trichloride or nitric acid ruthenium for noble metal active component Ru；
4. catalyst precursor C1 is impregnated into noble metal salt aqueous solution 10~30 minutes, afterwards solid-liquor separation, solid phase is collected,
110~140 DEG C of dryings 10~18 hours, then it is calcined 4~6 hours at 400~600 DEG C, obtains catalyst precursor.Wherein,
In dipping process, the precursor water solution of noble metal active component ruthenium is 1 with catalyst precursor C1 mass ratio：0.5~
1.2。
Activating treatment method：
It is 600~1500h in 200~450 DEG C, gas volume air speed under the conditions of fixed bed reaction-1、H2/N2Volume ratio
For 0.4~1.5:1st, under conditions of 0.1~0.4MPa of pressure, pre-activate is carried out 2~6 hours to catalyst precursor, obtains this
The catalyst of trace sulfide in the essence removing benzene of invention.
The specific synthetic method and step of the catalyst of the present invention can also be by those skilled in the art according to disclosed above
It is changed with reference to prior art, in above-mentioned specific steps, processing method and the illustrative description of parameter and following examples
Specific descriptions be not to be construed as be used for limit protection scope of the present invention.Wherein the concentration of specific embodiment, temperature, when
Between, pressure and other parameters and concrete application conditions have relation, be not described further herein.
With reference to specific embodiment, the present invention is expanded on further.Those skilled in the art can be as disclosed by this specification
Content understand and grasp the present invention other advantages and effect.The present invention can also be by way of a different and different embodiment
It is embodied or practiced, the various details in this specification can also be based on different viewpoints and application, without departing from the present invention
Spirit under carry out various modifications or alterations.It should be understood that following examples are only used for further illustrating the present invention, rather than
Limit protection scope of the present invention.The modifications and adaptations that technical staff makes according to the present invention in actual applications, still fall within this
The protection domain of invention.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
There can also be other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described；Moreover, unless otherwise indicated, the numbering of various method steps is only to differentiate the convenient tool of various method steps, Er Feiwei
Limit the ordering of various method steps or limit the enforceable scope of the present invention, its relativeness is altered or modified, in nothing
In the case of essence change technology contents, when being also considered as the enforceable category of the present invention.
Al2O3Carrier prepares embodiment
Al2O3The preparation of carrier：It is 300~400 mesh γ types Al to weigh granularity prepared by 450 DEG C of roastings respectively2O314Kg、
Granularity prepared by 850 DEG C of roastings is 300~400 mesh ρ types Al2O3Granularity prepared by 6.0Kg, 1100 DEG C of roastings is 300~400 mesh α
Type Al2O39.0Kg, 0.9Kg graphite, 0.6Kg sesbania powders, are stirred 40min in kneader；0.6Kg 63% is weighed respectively
Salpeter solution and 9.5Kg deionized waters, above-mentioned powder mixture is added after salpeter solution and deionized water are well mixed, then
Insert in kneader, after kneader mediates 150min, the column that extruded moulding obtains φ 2.0mm, length is 30~60mm carries
Body, under 450 DEG C of temperature conditionss, it is calcined 4 hours, Al is made2O3Carrier, shaped screening obtain φ 2.0mm, a length of 2~3mm
Column Al2O3Carrier, in case catalyst preparation uses.In addition, in the present embodiment, the diameter of the column like catalyst carrier is in 1.5-
The purpose of the present invention can be achieved in 2.5mm.Also, it is suitable that those skilled in the art can determine according to the size of reactor
Catalyst size, it is above-mentioned to enumerate the number range for being not used in and limiting suitable catalyst size.
Embodiment 1
By 26.5g Fe (NO3)3.9H2O is dissolved in 115ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, by 150g
The Al of above-mentioned preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 6 hours under stirring condition, is filtered and is collected solid phase,
Dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 4.7g RuCl3.nH2O is dissolved in 110ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 30min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 400 DEG C, gas is switched into H2Flow is 960ml/min, N2Throughput is 1400ml/min, is 0.3MPa, temperature in pressure
Under the conditions of 400 DEG C of degree, kept for 5 hours, obtain the catalyst of trace sulfide in essence removing benzene.It is living in the catalyst prod
The content that property component Ru content is 1.0%, Fe is 3.0%.
Under the conditions of fixed bed reaction, 140 DEG C, 0.6MPa, by containing thiophene be 0.84ppm liquid benzene with 3.5ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.72g (thiophene)/Kg (catalyst).
Embodiment 2
By 58.5g Fe (NO3)3.9H2O is dissolved in 150ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, by 140g
The Al of above-mentioned preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 2 hours under stirring condition, is filtered and is collected solid phase,
Dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 3.1g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 300 DEG C, gas is switched into H2Flow is 960ml/min, N2Throughput is 1400ml/min, is 0.3MPa, temperature in pressure
Under the conditions of 300 DEG C of degree, kept for 6 hours, obtain the catalyst of trace sulfide in essence removing benzene.It is living in the catalyst prod
The content that property component Ru content is 0.55%, Fe is 3.9%.
Under the conditions of fixed bed reaction, 140 DEG C, 0.6MPa, by containing thiophene be 0.84ppm liquid benzene with 3.5ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.6g (thiophene)/Kg (catalyst).
Embodiment 3
By 160g Fe (NO3)3.9H2O is dissolved in 150ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, by 130g
The Al of above-mentioned preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 6 hours under stirring condition, is filtered and is collected solid phase,
Dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 25g RuCl3.nH2O is dissolved in 120ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 400 DEG C, gas is switched into H2Flow is 960ml/min, N2Throughput is 1400ml/min, is 0.3MPa, temperature in pressure
Under the conditions of 400 DEG C of degree, kept for 3 hours, obtain the catalyst of trace sulfide in essence removing benzene.It is living in the catalyst prod
The content that property component Ru content is 4.75%, Fe is 14.6%.
Under the conditions of fixed bed reaction, 140 DEG C, 0.6MPa, by containing thiophene be 0.84ppm liquid benzene with 3.5ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.8g (thiophene)/Kg (catalyst).
Embodiment 4
By 32.5g Cu (NO3)2.3H2O is dissolved in 130ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by 150g
The Al of preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 2 hours under stirring condition, is filtered and is collected solid phase, 120
Dried 12 hours under the conditions of DEG C, be then calcined 4 hours under 480 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 4.0g RuCl3.nH2O is dissolved in 120ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 15min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 380 DEG C, gas is switched into H2Flow is 1050ml/min, N2Throughput is 1000ml/min, pressure be 0.2MPa,
Under the conditions of 380 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content that active component Ru content is 0.65%, Cu is 3.81%.
Under the conditions of fixed bed reaction, 155 DEG C, 0.9MPa, by containing thiophene be 0.87ppm liquid benzene with 3.2ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.65g (thiophene)/Kg (catalyst).
Embodiment 5
By 35.0g Cu (NO3)2.3H2O is dissolved in 140ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by 140g
The Al of preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 2 hours under stirring condition, is filtered and is collected solid phase, 120
Dried 12 hours under the conditions of DEG C, be then calcined 4 hours under 480 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 3.15g RuCl3.nH2O is dissolved in 120ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by catalyst
Presoma C1 is put into the ruthenium trichloride aqueous solution of preparation, impregnates 15min under stirring condition, is filtered and is collected solid phase, at 120 DEG C
Under the conditions of dry 12 hours, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 380 DEG C, gas is switched into H2Flow is 1050ml/min, N2Throughput is 1000ml/min, pressure be 0.2MPa,
Under the conditions of 380 DEG C of temperature, kept for 5 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content that active component Ru content is 0.5%, Cu is 3.0%.
Under the conditions of fixed bed reaction, 155 DEG C, 0.9MPa, by containing thiophene be 0.87ppm liquid benzene with 3.2ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.63g (thiophene)/Kg (catalyst).
Embodiment 6
By 62.0g Cu (NO3)2.3H2O is dissolved in 130ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by 120g
The Al of preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 6 hours under stirring condition, is filtered and is collected solid phase, 120
Dried 12 hours under the conditions of DEG C, be then calcined 4 hours under 480 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 37.0g RuCl3.nH2O is dissolved in 120ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by catalyst
Presoma C1 is put into the ruthenium trichloride aqueous solution of preparation, impregnates 30min under stirring condition, is filtered and is collected solid phase, at 120 DEG C
Under the conditions of dry 12 hours, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 350 DEG C, gas is switched into H2Flow is 1050ml/min, N2Throughput is 1000ml/min, pressure be 0.2MPa,
Under the conditions of 350 DEG C of temperature, kept for 6 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content that active component Ru content is 4.8%, Cu is 14.9%.
Under the conditions of fixed bed reaction, 155 DEG C, 0.9MPa, by containing thiophene be 0.87ppm liquid benzene with 3.2ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.80g (thiophene)/Kg (catalyst).
Embodiment 7
By 40g Zn (NO3)2.6H2O is dissolved in 150ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, by 150g
State the Al of preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 2 hours under stirring condition, is filtered and is collected solid phase,
Dried 15 hours under the conditions of 120 DEG C, be then calcined 4 hours under 400 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 3.8g RuCl3.nH2O is dissolved in 110ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 15min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 240 DEG C, gas is switched into H2Flow is 980ml/min, N2Throughput is 1100ml/min, is 0.4MPa, temperature in pressure
Under the conditions of 240 DEG C of degree, kept for 4 hours, obtain the catalyst of sulfide in essence removing benzene.In the catalyst prod, activearm
It is 3.3% to divide the content that Ru content is 0.7%, Zn.
Under the conditions of fixed bed reaction, 160 DEG C, 1.1MPa, by containing thiophene be 0.75ppm liquid benzene with 3.6ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.63g (thiophene)/Kg (catalyst).
Embodiment 8
By 38.5g Zn (NO3)2.6H2O is dissolved in 150ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, by 140g
The Al of above-mentioned preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 2 hours under stirring condition, is filtered and is collected solid phase,
Dried 15 hours under the conditions of 120 DEG C, be then calcined 4 hours under 400 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 3.5g RuCl3.nH2O is dissolved in 110ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 450 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 240 DEG C, gas is switched into H2Flow is 980ml/min, N2Throughput is 1100ml/min, is 0.4MPa, temperature in pressure
Under the conditions of 240 DEG C of degree, kept for 6 hours, obtain the catalyst of sulfide in essence removing benzene.In the catalyst prod, activearm
It is 3.0% to divide the content that Ru content is 0.5%, Zn.
Under the conditions of fixed bed reaction, 160 DEG C, 1.1MPa, by containing thiophene be 0.75ppm liquid benzene with 3.6ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.6g (thiophene)/Kg (catalyst).
Embodiment 9
By 225g Zn (NO3)2.6H2O is dissolved in 150ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, by 150g
The Al of above-mentioned preparation2O3Carrier is put into the solution of above-mentioned preparation, after being impregnated 6 hours under stirring condition, is filtered and is collected solid phase,
Dried 15 hours under the conditions of 120 DEG C, be then calcined 6 hours under 400 DEG C of temperature conditionss, obtain catalyst precursor C1.
By 35g RuCl3.nH2O is dissolved in 110ml deionized waters, is placed in 40 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 240 DEG C, gas is switched into H2Flow is 980ml/min, N2Throughput is 1100ml/min, is 0.4MPa, temperature in pressure
Under the conditions of 240 DEG C of degree, kept for 6 hours, obtain the catalyst of sulfide in essence removing benzene.In the catalyst prod, activearm
It is 13.8% to divide the content that Ru content is 4.3%, Zn.
Under the conditions of fixed bed reaction, 160 DEG C, 1.1MPa, by containing thiophene be 0.75ppm liquid benzene with 3.6ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.8g (thiophene)/Kg (catalyst).
Embodiment 10
By 27.5g Fe (NO3)3.9H2O、18.0g Cu(NO3)2.3H2O is dissolved in 130ml deionized waters, is placed on 45
In DEG C water bath with thermostatic control, by the Al of the above-mentioned preparations of 150g2O3Carrier is put into the solution of above-mentioned preparation, is impregnated 2 hours under stirring condition
Afterwards, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
Catalyst precursor C1.
By 5.2g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 10min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 400 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 400 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content that the content that active component Ru content is 0.65%, Fe is 2.0%, Cu is 1.5%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.65g (thiophene)/Kg (catalyst).
Embodiment 11
By 28.0g Fe (NO3)3.9H2O、19.5g Cu(NO3)2.3H2O is dissolved in 130ml deionized waters, is placed on 45
In DEG C water bath with thermostatic control, by the Al of the above-mentioned preparations of 120g2O3Carrier is put into the solution of above-mentioned preparation, is impregnated 3 hours under stirring condition
Afterwards, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
Catalyst precursor C1.
By 4.8g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 350 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 450 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 450 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content sum that the content that the content that active component Ru content is 0.5%, Fe is 1.6%, Cu is 1.5%, Fe and Cu is
3.1%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.63g (thiophene)/Kg (catalyst).
Embodiment 12
By 77.0g Fe (NO3)3.9H2O、73.0g Cu(NO3)2.3H2O is dissolved in 130ml deionized waters, is placed on 45
In DEG C water bath with thermostatic control, by the Al of the above-mentioned preparations of 140g2O3Carrier is put into the solution of above-mentioned preparation, is impregnated 5 hours under stirring condition
Afterwards, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
Catalyst precursor C1.
By 29.5g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by catalyst
Presoma C1 is put into the ruthenium trichloride aqueous solution of preparation, impregnates 20min under stirring condition, is filtered and is collected solid phase, at 120 DEG C
Under the conditions of dry 12 hours, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 400 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 400 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content sum that the content that the content that active component Ru content is 4.2%, Fe is 6.1%, Cu is 7.0%, Fe and Cu is
13.1%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.77g (thiophene)/Kg (catalyst).
Embodiment 13
By 21.0g Fe (NO3)3.9H2O、24.0g Zn(NO3)2.6H2O is dissolved in 130ml deionized waters, is placed on 45
In DEG C water bath with thermostatic control, by the Al of the above-mentioned preparations of 120g2O3Carrier is put into the solution of above-mentioned preparation, is impregnated 2 hours under stirring condition
Afterwards, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
Catalyst precursor C1.
By 4.1g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 350 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 450 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 450 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content sum that the content that the content that active component Ru content is 0.54%, Fe is 1.7%, Zn is 1.9%, Fe and Zn is
3.6%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.6g (thiophene)/Kg (catalyst).
Embodiment 14
By 101.0g Fe (NO3)3.9H2O、108.0g Zn(NO3)2.6H2O is dissolved in 130ml deionized waters, is placed on
In 45 DEG C of waters bath with thermostatic control, by the Al of the above-mentioned preparations of 120g2O3Carrier is put into the solution of above-mentioned preparation, and it is small that 6 are impregnated under stirring condition
Shi Hou, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
To catalyst precursor C1.
By 36.5g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by catalyst
Presoma C1 is put into the ruthenium trichloride aqueous solution of preparation, impregnates 20min under stirring condition, is filtered and is collected solid phase, at 120 DEG C
Under the conditions of dry 12 hours, be then calcined 3 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 400 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 400 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content sum that the content that the content that active component Ru content is 4.3%, Fe is 7.2%, Zn is 7.5%, Fe and Zn is
14.7%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.75g (thiophene)/Kg (catalyst).
Embodiment 15
By 13.9g Cu (NO3)2.3H2O、22.4g Zn(NO3)2.6H2O is dissolved in 130ml deionized waters, is placed on 45
In DEG C water bath with thermostatic control, by the Al of the above-mentioned preparations of 120g2O3Carrier is put into the solution of above-mentioned preparation, is impregnated 2 hours under stirring condition
Afterwards, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
Catalyst precursor C1.
By 4.2g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 380 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 380 DEG C of temperature, kept for 6 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content sum that the content that the content that active component Ru content is 0.58%, Cu is 1.4%, Zn is 1.8%, Cu and Zn is
3.2%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.62g (thiophene)/Kg (catalyst).
Embodiment 16
By 84.5g Cu (NO3)2.3H2O、109.5g Zn(NO3)2.6H2O is dissolved in 130ml deionized waters, is placed on
In 45 DEG C of waters bath with thermostatic control, by the Al of the above-mentioned preparations of 130g2O3Carrier is put into the solution of above-mentioned preparation, and it is small that 6 are impregnated under stirring condition
Shi Hou, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, be then calcined 4 hours, obtain under 450 DEG C of temperature conditionss
To catalyst precursor C1.
By 34.0g RuCl3.nH2O is dissolved in 125ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by catalyst
Presoma C1 is put into the ruthenium trichloride aqueous solution of preparation, impregnates 30min under stirring condition, is filtered and is collected solid phase, at 120 DEG C
Under the conditions of dry 12 hours, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 400 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 400 DEG C of temperature, kept for 6 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content sum that the content that the content that active component Ru content is 4.1%, Cu is 6.9%, Zn is 7.5%, Cu and Zn is
14.4%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.76g (thiophene)/Kg (catalyst).
Embodiment 17
By 68.0g Cu (NO3)2.3H2O、96.0g Zn(NO3)2.6H2O、110.0g Fe(NO3)3.9H2O is dissolved in
In 150ml deionized waters, it is placed in 45 DEG C of waters bath with thermostatic control, by the Al of the above-mentioned preparations of 150g2O3Carrier is put into the molten of above-mentioned preparation
In liquid, after being impregnated 6 hours under stirring condition, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, then at 450 DEG C
It is calcined 5 hours under temperature conditionss, obtains catalyst precursor C1.
By 36.5g RuCl3.nH2O is dissolved in 140ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, by catalyst
Presoma C1 is put into the ruthenium trichloride aqueous solution of preparation, impregnates 30min under stirring condition, is filtered and is collected solid phase, at 120 DEG C
Under the conditions of dry 12 hours, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 450 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 450 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content that the content that the content that active component Ru content is 4.7%, Cu is 4.6%, Zn is 4.5%, Fe is 5.8%, Cu, Zn
Content sum with Fe is 14.9%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.77g (thiophene)/Kg (catalyst).
Embodiment 18
By 17.8g Cu (NO3)2.3H2O、18.5g Zn(NO3)2.6H2O、56.5g Fe(NO3)3.9H2O is dissolved in 130ml
In deionized water, it is placed in 45 DEG C of waters bath with thermostatic control, by the Al of the above-mentioned preparations of 130g2O3Carrier is put into the solution of above-mentioned preparation,
After being impregnated 3 hours under stirring condition, filter and collect solid phase, dried 12 hours under the conditions of 120 DEG C, then in 450 DEG C of temperature
Under the conditions of be calcined 4 hours, obtain catalyst precursor C1.
By 4.5g RuCl3.nH2O is dissolved in 130ml deionized waters, is placed in 45 DEG C of waters bath with thermostatic control, before catalyst
Drive body C1 to be put into the ruthenium trichloride aqueous solution of preparation, impregnate 20min under stirring condition, filter and collect solid phase, in 120 DEG C of bars
Dried 12 hours under part, be then calcined 4 hours under 380 DEG C of temperature conditionss, obtain catalyst precursor C2.
140ml catalyst precursors are fitted into φ 17 × 1800 fixed bed reactors, using N2Purging, treats temperature liter
During to 450 DEG C, gas is switched into H2Flow is 1000ml/min, N2Throughput is 1200ml/min, pressure be 0.4MPa,
Under the conditions of 450 DEG C of temperature, kept for 4 hours, obtain the catalyst of trace sulfide in essence removing benzene.In the catalyst prod,
The content that the content that the content that active component Ru content is 0.53%, Cu is 1.65%, Zn is 1.38%, Fe is 4.6%,
Cu, Zn and Fe content sum are 7.63%.
Under the conditions of fixed bed reaction, 150 DEG C, 0.7MPa, by containing thiophene be 0.92ppm liquid benzene with 4.0ml/
Min speed squeezes into reactor, under experimental conditions, can't detect outlet benzene using gas chromatographicanalyzer and contains any thiophene
Class sulfide, under experimental conditions, the Sulfur capacity for measuring catalyst are 0.65g (thiophene)/Kg (catalyst).
The catalytic adsorption desulphurization catalyst that the above embodiment of the present invention provides, has very high work under experimental conditions
Property, effectively essence sulfide micro in benzene can be removed, the catalyst can be such that the content of sulfide in benzene raw materials is reduced by ppm levels
To ppb levels, it can be applied to during the raw material pretreatment process of benzene selective hydrogenation reaction, can effectively extend benzene hydrogenation mistake
The service life of catalyst in journey.
It is at present to use from the palladium catalyst employed in external introduce technology to be used for what is used in industrialized production
Micro thiophene-type sulfide in essence removing benzene, because precious metal palladium is expensive, price is 8~10 times of ruthenium, therefore is developed
The fine desulfurization catalyst of replacement turns into the bottleneck for reducing enterprise's production cost.
The present inventor combine in the past the field achievement in research and on the basis of substantial amounts of experimental study, find ruthenium load
There is desulfurization performance more more preferable than palladium on suitable carrier, tested by lab pilot plant and industrial side line, show the present invention
Palladium catalyst of the load ruthenium catalyst completely employed in alternative former patented technology.
The useful achievement major embodiment of the present invention：(a) production cost of enterprise will be greatly reduced using catalyst of the present invention,
Significantly improve the economic benefit of enterprise；(b) catalyst of the present invention is to propose to remove the thiophene-type sulfide in benzene for essence first,
Because the boiling point of the thiophene-type sulfide in benzene approaches with benzene, therefore remove more difficult.
Under the teaching of the present invention and above-described embodiment, those skilled in the art are easy to it is envisioned that cited by the present invention
Each raw material and method can realize that the present invention, and the bound value of each raw material and technique, interval value can realize this hair
It is bright, embodiment numerous to list herein.
Claims (10)
1. the catalyst of trace sulfide in a kind of essence removing benzene, including carrier and load active component on the carrier,
Characterized in that, the carrier is to contain 40 ~ 70% γ types Al2O3, 20 ~ 50% ρ types Al2O3With 20 ~ 50% α types Al2O3It is mixed
Close Al2O3Carrier, and the carrier is 1.5 ~ 2.5mm of φ, a length of 2 ~ 3mm cylindrical particle, the active component is by mass content
Account for the noble metal active component ruthenium of whole catalyst quality 0.5 ~ 5.0% and mass content accounts for whole catalyst quality 3.0 ~ 16.0%
Base metal active component M composition, wherein M be Fe, Cu, Zn in one or more, the catalyst is in fixed bed reaction
Under the conditions of, 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, 0.5 ~ 4.0h of benzene liquid volume air speed-1, benzene feed is the ppm orders of magnitude containing thiophene
Under conditions of, its Sulfur capacity >=0.6g thiophene/Kg catalyst.
2. the preparation method of the catalyst of trace sulfide in the essence removing benzene described in a kind of claim 1, it is characterised in that bag
Include following steps：
（1）Using program infusion process successively in the Al2O3Supported on carriers base metal active constituent M and noble metal active group
Divide Ru presoma, obtain catalyst precursor；
（2）It is 600 ~ 1500h in 200 ~ 450 DEG C, gas volume air speed under the conditions of fixed bed reaction-1、H2/N2Volume ratio is
0.4~1.5:1st, under conditions of 0.1 ~ 0.4MPa of pressure, pre-activate is carried out 2 ~ 6 hours to the catalyst precursor, obtained described
The catalyst of trace sulfide in essence removing benzene.
3. the preparation method of the catalyst of trace sulfide in essence removing benzene as claimed in claim 2, it is characterised in that in institute
State step（1）Also include before：It is prepared by the following method the Al2O3Carrier：
First, by graphite, sesbania powder, 300 ~ 400 mesh γ types Al2O3Powder, ρ types Al2O3Powder and α types Al2O3Powder is well mixed
To powder mixture, wherein γ types Al2O3Powder 40 ~ 70%, ρ types Al2O3Powder 20 ~ 50%, α types Al2O3Powder 20 ~ 50%, graphite 1 ~ 4%,
Sesbania powder 1 ~ 4%；
Then, by quality for the powder mixture quality 1 ~ 4%, concentration for 45 ~ 63% salpeter solution add quality be institute
In 30 ~ 50% deionized water for stating powder mixture quality, after stirring, add in the powder mixture, in room temperature bar
Mediated 2 ~ 4 hours under part；
Afterwards, to the mixture after above-mentioned kneading, extruded moulding obtains 1.5 ~ 2.5mm of φ, 30 ~ 60mm of length carrier, 400
Under ~ 600 DEG C of temperature conditionss, it is calcined 4 ~ 8 hours, is made and contains γ types Al2O3, ρ types Al2O3With α types Al2O3Mixing Al2O3Carry
Body, and shaped screening obtains 1.5 ~ 2.5mm of φ, a length of 2 ~ 3mm column Al2O3Carrier.
4. the preparation method of the catalyst of trace sulfide in essence removing benzene as claimed in claim 3, it is characterised in that described
The γ types Al of 300 ~ 400 mesh2O3Powder, ρ types Al2O3Powder and α types Al2O3Powder is made by the following method：By 300 ~ 400 mesh activity
Al2O3Powder calcines 4 ~ 8 hours under 450 ~ 600 DEG C, 800 ~ 900 DEG C, 1100 ~ 1200 DEG C of temperature conditionss respectively, it is made 300 respectively ~
400 mesh γ types Al2O3, ρ types Al2O3With α types Al2O3Powder.
5. the preparation method of the catalyst of trace sulfide in essence removing benzene as claimed in claim 2, it is characterised in that described
Step（1）Comprise the following steps：
（1.1）By the Al2O3Carrier impregnation is 0.5 ~ 50% base metal active component M's in 40 ± 5 DEG C, mass concentration
2 ~ 6 hours in precursor water solution, solid-liquor separation afterwards collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~
600 DEG C are calcined 4 ~ 6 hours, obtain catalyst precursor C1；Wherein, in dipping process, base metal active component M presoma
The aqueous solution and carrier Al2O3Mass ratio be 1：0.8~1.5；
（1.2）By the noble metal active component ruthenium that catalyst precursor C1 is immersed in 40 ± 5 DEG C, mass concentration is 0.5 ~ 3.5%
Precursor water solution in 10 ~ 30 minutes, solid-liquor separation afterwards collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, Ran Hou
300 ~ 600 DEG C are calcined 4 ~ 6 hours, obtain catalyst precursor；Wherein, in dipping process, the forerunner of noble metal active component ruthenium
The body aqueous solution and catalyst precursor C1 mass ratio are 1：0.5~1.2.
6. the preparation method of the catalyst of trace sulfide in the essence removing benzene as described in claim 2 or 5, it is characterised in that
The step（1）In, the presoma of ruthenium trichloride or nitric acid ruthenium for noble metal active component ruthenium is used, using ferric nitrate, nitric acid
Copper, zinc nitrate, ferric trichloride, copper sulphate or zinc sulfate are base metal active component M presoma.
7. the preparation method of the catalyst of trace sulfide is made in the essence removing benzene any one of a kind of claim 3-4
Contain 40 ~ 70% γ types Al2O3, 20 ~ 50% ρ types Al2O3With 20 ~ 50% α types Al2O3The Al2O3Carrier.
8. in the essence removing benzene any one of a kind of claim 5 made from the preparation method of the catalyst of trace sulfide
The catalyst precursor C1.
9. the preparation method of the catalyst of trace sulfide is made in the essence removing benzene any one of a kind of claim 2-6
The catalyst precursor, it is characterised in that be prepared via a method which to obtain：
（1.1）By the Al2O3Carrier impregnation is 0.5 ~ 50% base metal active component M's in 40 ± 5 DEG C, mass concentration
2 ~ 6 hours in precursor water solution, solid-liquor separation afterwards collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, then 400 ~
600 DEG C are calcined 4 ~ 6 hours, obtain catalyst precursor C1；Wherein, in dipping process, base metal active component M presoma
The aqueous solution and carrier Al2O3Mass ratio be 1：0.8~1.5；
（1.2）By the noble metal active component ruthenium that catalyst precursor C1 is immersed in 40 ± 5 DEG C, mass concentration is 0.5 ~ 3.5%
Precursor water solution in 10 ~ 30 minutes, solid-liquor separation afterwards collects solid phase, 110 ~ 140 DEG C of dryings 10 ~ 18 hours, Ran Hou
300 ~ 600 DEG C are calcined 4 ~ 6 hours, obtain catalyst precursor；Wherein, in dipping process, the forerunner of noble metal active component ruthenium
The body aqueous solution and catalyst precursor C1 mass ratio are 1：0.5~1.2.
10. the application of the catalyst of trace sulfide in the essence removing benzene described in a kind of claim 1, it is characterised in that solid
Under fixed bed reaction condition, 120 ~ 180 DEG C, 0.4 ~ 1.5MPa, 0.5 ~ 4.0h of benzene liquid volume air speed-1Under the conditions of, thiophene will be contained
Enter reactor for the benzene of the ppm orders of magnitude, thiophenes sulfides are can't detect in the benzene in exit.
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| CN112547111A (en) * | 2020-12-31 | 2021-03-26 | 河南神马催化科技股份有限公司 | Ruthenium catalyst for removing trace sulfide in benzene |
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| CN108212189A (en) * | 2016-12-09 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of transition-metal catalyst of minute amount of noble metal modification and its preparation and application |
| CN111905755B (en) * | 2020-07-16 | 2022-07-05 | 浙江恒逸石化研究院有限公司 | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof |
| CN112547112B (en) * | 2020-12-31 | 2021-08-27 | 河南神马催化科技股份有限公司 | Palladium catalyst for removing trace sulfide in benzene |
| CN112547113B (en) * | 2020-12-31 | 2021-08-27 | 河南神马催化科技股份有限公司 | Preparation method of noble metal @ ZSM core-shell structure catalyst |
| CN112958083A (en) * | 2021-03-16 | 2021-06-15 | 河南神马催化科技股份有限公司 | Ruthenium catalyst for removing trace sulfide in benzene |
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| CN102688766A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing 1,3-cyclohexanebis(methylamine) by m-xylylenediamine hydrogenation under ammonia reaction conditions |
| CN104014337B (en) * | 2014-06-10 | 2017-02-01 | 中国科学院山西煤炭化学研究所 | Catalyst for selective hydrogenation and olefin removal of reformed generated oil as well as preparation method and application |
| CN104307464B (en) * | 2014-10-24 | 2017-02-22 | 上海迅凯新材料科技有限公司 | Ruthenium-based adsorbent for deeply removing thiophene of benzene as well as preparation method and application of ruthenium-based adsorbent |
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