CN106140176A - The catalyst system of sulfur-bearing hydrocarbon desulfurization and the method for sulfur-bearing hydrocarbon desulfurization - Google Patents
The catalyst system of sulfur-bearing hydrocarbon desulfurization and the method for sulfur-bearing hydrocarbon desulfurization Download PDFInfo
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- CN106140176A CN106140176A CN201510209448.9A CN201510209448A CN106140176A CN 106140176 A CN106140176 A CN 106140176A CN 201510209448 A CN201510209448 A CN 201510209448A CN 106140176 A CN106140176 A CN 106140176A
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Abstract
The present invention relates to desulfuration field, specifically disclose the catalyst system of a kind of sulfur-bearing hydrocarbon desulfurization, this catalyst system is for the method for sulfur-bearing hydrocarbon desulfurization.This catalyst system includes desulfurizing assistant agent and ordered structure catalyst；The active component coating of described ordered structure catalyst contains active metal and the substrate of 10-70 weight % of 30-90 weight %；Described desulfurizing assistant agent contains at least one metal-oxide, 0.5-10 weight % rare earth oxide, 5-35 weight % silica source and IIB, the VB of 30-89.5 weight % in the Group IVB of 5-35 weight % and IVA race and the oxide of at least one metal in group vib, and described desulfurizing assistant agent is the microsphere of mean diameter 20-200 micron；The weight ratio of the active component coating of described desulfurizing assistant agent and described ordered structure catalyst is 1-9:1.The catalyst system that the present invention provides can have the most desulphurizing activated and desulfurization stability.
Description
Technical field
The present invention relates to catalyst system and the method for sulfur-bearing hydrocarbon desulfurization of sulfur-bearing hydrocarbon desulfurization, specifically, relate to
And the catalyst system of a kind of sulfur-bearing hydrocarbon desulfurization, this catalyst system is for the method for sulfur-bearing hydrocarbon desulfurization.
Background technology
Sulfur in vehicle fuel, produces oxysulfide after burning.This material can suppress vehicle exhaust converter
In noble metal catalyst activity and can be allowed to occur irreversibly to be poisoned, it is impossible to realize catalyzed conversion vapour
The effect of the toxic gas in tail gas, causes in vehicle exhaust containing unburned non-methane hydrocarbon and nitrogen
Oxide and carbon monoxide.And the toxic gas of these discharges is easily formed photochemistry cigarette by hydrophilic dye
Mist, causes acid rain.And oxysulfide itself is also the one of the main reasons forming acid rain.
Along with people's pay attention to day by day to environmental conservation, environmental regulation is the strictest, and reduce gasoline and
Sulfur content in diesel oil is considered as one of most important measure improving air quality.As a example by gasoline, Europe
Alliance specifies that in the Europe V gasoline standard of enforcement in 2010 sulfur content is less than 10 μ g/g.The vapour that China is existing
Oil product standard GB 17930-2011 " motor petrol " requirement to 2013 on December 31, in gasoline
Sulfur content must drop to 50 μ g/g.And gasoline quality standard in the future also can be stricter.
The main method of the desulfurization of fuel oil is hydrodesulfurization.But along with the increasingly stringent of standard of fuel, hydrogenation
The degree of depth improves, and needs the harsher the most higher reaction pressure of reaction condition etc..Additionally for gasoline, by
In containing substantial amounts of alkene, improving hydrogenation severity and will cause higher loss of octane number, therefore some are new
Sulfur method continue to bring out, be the most especially concerned by people most with absorption desulfurization.
US7427581, US7182918, US6869522 and US6274533 etc. disclose employing absorption
Agent carries out desulfurization to lightweight sulfur-bearing hydrocarbon under hydro condition, has desulfurization depth height, hydrogen low, the octane number of consumption
The features such as loss is few, can produce the fuel oil that sulfur content is 30 below μ g/g.Sorbent used with oxygen
Changing zinc, Silicon stone and alumina mixture is carrier, and wherein zinc oxide accounts for 10-90 weight %, Silicon stone accounts for 5-85
Weight %, aluminium oxide account for 5-30 weight %；Load active component be as-reduced metal, can be cobalt,
At least one in copper, manganese, tungsten, stannum, nickel, ferrum, molybdenum, silver and vanadium.Adsorbent 0.1-10.3MPa,
37.7-537.7 DEG C, weight (hourly) space velocity (WHSV) be 0.5-50h-1Under conditions of facing hydrogen, the sulfur in oil product is captured
Be combined with zinc oxide on adsorbent, then the sulfur removing that oxidized regeneration will combine on zinc oxide.After regeneration
Adsorbent is recycled the most again.The method recycles adsorbent, needs adsorbent frequent
Ground carries out oxidation regeneration-reduction, so that zinc oxide component desulfurization regeneration therein, and the work in adsorbent
Property component need not regeneration.But, in oxidation regeneration-reduction process frequently, as active component
Metal can assemble, and reduction temperature limited by zinc oxide sublimation temperature also result in activity gold
Belong to reduction not thorough, make the adsorbent desulphurizing activated decline during recycling, the inactivation of adsorbent
Speed is higher, affects the implementation result of sulfur-bearing hydrocarbon desulfurization.
As can be seen here, although absorption desulfurization can have a good deep desulfuration, but the desulfurization of actual application
Activity and desulfurization stability yet suffer from problem.
Accordingly, it would be desirable to new sulfur-bearing hydrocarbon desulfurization method, to overcome the defect of prior art.
Summary of the invention
The invention aims to overcome the defect of prior art, it is provided that the catalyst of sulfur-bearing hydrocarbon desulfurization
System and the method for sulfur-bearing hydrocarbon desulfurization.
To achieve these goals, the present invention provides the catalyst system of a kind of sulfur-bearing hydrocarbon desulfurization, this catalysis
Agent system includes desulfurizing assistant agent and ordered structure catalyst；Described ordered structure catalyst includes ordered structure
Carrier and the active component coating being distributed in carrier inner surface and/or outer surface, with described active component coating
Gross weight on the basis of, described active component coating contains active metal and the 10-70 of 30-90 weight %
The substrate of weight %, described active metal is the metal of VIIB race and/or VIII；Help with described desulfurization
On the basis of the gross weight of agent, described desulfurizing assistant agent contains in IVA race and the Group IVB of 5-35 weight %
At least one metal-oxide, the rare earth oxide of 0.5-10 weight %, the silica source of 5-35 weight %
With the oxide of at least one metal in IIB, VB of 30-89.5 weight % and group vib, described de-
Sulfur auxiliary agent is the microsphere of mean diameter 20-200 micron；Described desulfurizing assistant agent is catalyzed with described ordered structure
The weight ratio of the active component coating of agent is 1-9:1.
A kind of method that present invention also offers sulfur-bearing hydrocarbon desulfurization, the method includes: anti-in sulfur-bearing hydrocarbon desulfurization
Under the conditions of Ying, in sulfur-bearing hydrocarbon desulfurization reactor, sulfur-bearing hydrocarbon be contacted with catalyst system with hydrogen donor；
Wherein, the catalyst system that described catalyst system provides for the present invention, the rule in described catalyst system
Whole structure catalyst is presented in beds, and the desulfurizing assistant agent in described catalyst system is with stream
The form changed passes through beds.
The present invention compared with prior art, has a following technique effect:
(1) active component is distributed in ordered structure catalyst inside/outside surface in the way of coating, in coating
Active metal dispersion is higher, contacts easily with desulfurizing assistant agent, beneficially catalyst and the collaborative work of auxiliary agent
With performance；
(2) active component need not repeated regeneration after carrying out reduction, reduces the required absorption of removing unit sulfur content
The regeneration frequency of agent, not easily runs off, and improves activity and the stability of desulfuration adsorbent, can make with long period
With, reduce the unit consumption of catalyst；
(3) heap of desulfurizing assistant agent is than reducing, and has more preferable mobility, is advantageously implemented reaction-regeneration
Smooth and easy be carried out continuously.
(4) ordered structure carrier has the flowing of straight parallel pore passage structure, beneficially auxiliary agent.
(5) using non-al binder can avoid the generation of 23K-S, rare earth ion can be with binding agent
Interact, increase intensity and desulphurizing activated.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the device schematic diagram of sulfur-bearing hydrocarbon desulfurization.
Description of reference numerals
1 sulfur-bearing hydrocarbon desulfurization reaction 2 first pipeline 3 preheaters
Device
4 second pipeline 5 sulfur-bearing hydrocarbon and hydrogen donor feed pipe 6 desulfurizing assistant agent feed pipe
7 distributor 8 ordered structure catalyst 9 grids
10 reactor expanding reach 11 cyclone separator 12 exhaustors
13 charging aperture 14 discharge pipe 15 reactor receptors
16 the 3rd pipeline 17 the 4th pipeline 18 locking hoppers
19 displacement gas discharge pipe 20 the 5th pipeline 21 the 6th pipelines
22 regenerator feed tank 23 spent agent feed pipe 24 regeneration gas air inlet pipe
25 regenerator 26 smoke discharge pipe 27 regenerative agent discharge pipes
28 Regenerator receiver 29 the 7th pipeline 30 the 8th pipelines
31 reactor feed tank 32 the 9th pipelines
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, term ordered structure catalyst is used to refer to ordered structure carrier and be distributed in load
The catalyst of the active component coating of internal surface and/or outer surface；Ordered structure carrier is for having regular knot
The carrier of structure；Monolithic reactors is to have loaded ordered structure catalyst fixing as beds
Bed reactor.
The invention provides the catalyst system of a kind of sulfur-bearing hydrocarbon desulfurization, this catalyst system includes that desulfurization helps
Agent and ordered structure catalyst；Described ordered structure catalyst includes ordered structure carrier and is distributed in carrier
Inner surface and/or the active component coating of outer surface, on the basis of the gross weight of described active component coating,
Described active component coating contains active metal and the substrate of 10-70 weight % of 30-90 weight %, institute
State the metal that active metal is VIIB race and/or VIII；On the basis of the gross weight of described desulfurizing assistant agent,
Described desulfurizing assistant agent contain at least one metal-oxide in the IVA race of 5-35 weight % and Group IVB,
The rare earth oxide of 0.5-10 weight %, the silica source of 5-35 weight % and the IIB of 30-89.5 weight %,
The oxide of at least one metal in VB and group vib, described desulfurizing assistant agent is mean diameter 20-200
The microsphere of micron；The weight ratio of the active component coating of described desulfurizing assistant agent and described ordered structure catalyst
For 1-9:1, preferably 2-5:1, for example, 2:1,3:1 or 5:1.
According to the present invention, described ordered structure catalyst contains, and can to make organic sulfur conversion in sulfur-bearing hydrocarbon be sulfur
Change the active metal of hydrogen.Described active metal is made into active component coating formal distribution and carries at ordered structure
On body.Described active component coating is distributed in that the amount on ordered structure carrier can there is no particular limitation,
Under preferable case, on the basis of the gross weight of described ordered structure catalyst, described active component coating
Content is 3-30 weight %；Can preferably be 10-25 weight %.
According to the present invention, described ordered structure carrier may be used for providing in fixed bed reactors catalyst bed
Layer.This ordered structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, duct
Inwall on can be distributed catalyst coat, space, duct can serve as the flowing space of fluid.Preferably feelings
Under condition, described ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open.
Described ordered structure carrier can be the regular carrier of honeycomb fashion (the abbreviation honeycomb that cross section has cellular perforate
Carrier).
In the case of according to the invention it is preferred to, the hole density in the cross section of described ordered structure carrier is 20-900
Hole/square inch, preferably 20-400 hole/square inch, the percent opening of the section of described carrier is
20-80%.The shape in hole can be that square, wing square are (i.e. in square hole in four edges
There is the wing that vertical edges is inside heart position, its a length of square the length of side 1/5～2/5), equilateral triangle,
Regular hexagon, circular and corrugated in one.
In the case of according to the invention it is preferred to, described ordered structure carrier can be selected from cordierite honeycomb carrier,
Mullite honeycomb substrate, diamond honeycomb substrate, corundum honeycomb substrate, fused alumina zirconia honeycomb substrate, quartz
At least one in honeycomb substrate, nepheline honeycomb substrate and Anhydrite honeycomb substrate.
According to the present invention, described active component coating contains substrate and active metal.Preferably, with described
On the basis of the gross weight of active component coating, described active component coating contains the activity of 40-80 weight %
Metal and the substrate of 20-60 weight %.
In the present invention, described active component coating can be distributed on the duct inwall of ordered structure carrier.
Described active component coating by first preparing active component coating precursor, then can obtain through reduction treatment.
Active component coating precursor can obtain by the following method.
Method one: each component forming described substrate is mixed making beating with water by (1), forms substrate in slurry
The total content of each component can be 10-60 weight %, then this serosity is dried and roasting.Dry
Dry condition may include that temperature is 50-300 DEG C, preferably 100-200 DEG C, and the time is 0.5 hour
Above, preferably 1-10 hour；The condition of roasting may include that temperature is 300-700 DEG C, is preferably
400-500 DEG C, the time is more than 0.5 hour, preferably 1-10 hour；Obtain substrate；(2) to this
Active metal is introduced in substrate.The method of well known to a person skilled in the art can be used, such as, impregnate normal direction
Substrate introduces active metal, obtains catalyst.Can be with the solution containing active metallic compound or suspension
Impregnate described substrate.Described active metallic compound is to be changed into active metal oxygen under roasting condition
The material of compound, is reduced in the reduction treatment that reactive metal oxides describes below as activity gold
Belong to.Described active metallic compound can be selected from the acetate of active metal, carbonate, nitrate, sulfur
Hydrochlorate, rhodanate and oxide, and two of which or two or more mixture etc..Infusion process
Concrete operations condition and method are the most known to those skilled in the art, do not repeat them here；(3) incite somebody to action
To catalyst and aqueous solvent grind to form serosity, slurry solid content can be 20-40 weight %, to obtain final product
To described catalyst slurry, this catalyst slurry contains active metallic compound；(4) above-mentioned catalyst is used
Serosity coats described ordered structure carrier by cladding process and makes.Described cladding process can be water coating, leaching
Stain method or spray process.The concrete operations of coating are referred to the method described in CN 1199733C and carry out.
The ordered structure carrier of good for coating described catalyst slurry is dried and roasting, i.e. can be distributed in
Active component coating precursor on ordered structure carrier.The condition being dried includes: temperature is 90-130 DEG C,
Time is 3-10 hour, and more preferably temperature is 110-120 DEG C, and the time is 5-7 hour.The condition of roasting
Including: temperature 450-650 DEG C, the time is 8-20 hour.Containing living in described active component coating precursor
Property metal-oxide.
Method two: each component forming described substrate is mixed making beating with water by (1), forms substrate in slurry
The total content of each component can be 10-60 weight %, then this serosity is dried and roasting.Dry
Dry condition may include that temperature is 50-300 DEG C, preferably 100-200 DEG C, and the time is 0.5 hour
Above, preferably 1-10 hour；The condition of roasting may include that temperature is 300-700 DEG C, is preferably
400-500 DEG C, the time is more than 0.5 hour, preferably 1-10 hour；Obtain substrate；(2) should
Substrate grinds to form serosity, and slurry solid content can be 20-40 weight %, and with reference in CN 1199733C
Described method coating ordered structure carrier, then dry, roasting, condition ibid, obtains containing substrate
The ordered structure carrier of coating；(3) ordered structure containing matrix coating obtained to step (2) carries
Active metal is introduced on body.Substrate can be contained with the solution containing active metallic compound or suspension impregnation
The ordered structure carrier of coating is also dried and roasting, i.e. can obtain being distributed on ordered structure carrier
Active component coating precursor, containing reactive metal oxides in described active component coating precursor.It is dried
Condition includes: temperature is 90-130 DEG C, and the time is 3-10 hour, and more preferably temperature is 110-120 DEG C,
Time is 5-7 hour.The condition of roasting includes: temperature 450-650 DEG C, and the time is 8-20 hour.Institute
Stating active metallic compound is the material that can be changed into reactive metal oxides under roasting condition, activity
Reduction will be become active metal in the reduction treatment of description by metal-oxide below.Described active metal
Compound is selected from the acetate of active metal, carbonate, nitrate, sulfate, rhodanate and oxygen
Compound, and two of which or two or more mixture etc..The concrete operations condition of infusion process and method
The most known to those skilled in the art, do not repeat them here.
According to the present invention, described active component coating can be by reducing active component coating precursor
Process, the reactive metal oxides that active component coating precursor contains is changed into active metal and prepares.
Described reduction treatment can be carried out after preparing described active component coating precursor immediately, it is also possible to is using
Before (i.e. for desulfurization adsorb before) carry out.Owing to active metal easily aoxidizes, and before active component coating
Active metal in body exists in the form of an oxide, therefore for ease of transport, preferably by active component coating
Precursor reduction is carried out before carrying out desulfurization absorption.Described reduction treatment is in the oxide making active metal
Metal substantially exists with reduction-state, obtains the desulphurization catalyst of the present invention.Under preferable case, by activity
The condition that component coating precursor reduces in a hydrogen atmosphere includes: hydrogen content is going back of 10-60 volume %
Raw-gas, the temperature of reduction is 250-550 DEG C, and the pressure of reduction is 0.2-5MPa, and the time of reduction is
0.5-6 hour；The temperature preferably reduced is 300-450 DEG C, and the pressure of reduction is 0.5-3.5MPa, reduction
Time be 1-3 hour.
According to the present invention, described active metal can make organic sulfur conversion in sulfur-bearing hydrocarbon be hydrogen sulfide.Preferably
Ground, described active metal can be at least one in cobalt, nickel, ferrum and manganese.It is further preferred that described activity
Metal is nickel.
According to the present invention, described substrate can there is no particular limitation, can be well known in the art being used as
The material of substrate, can be various heat-resistant inorganic oxide, and under preferable case, described substrate is selected from oxidation
In aluminum, silicon oxide, amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide
At least one.
According to the present invention, described desulfurizing assistant agent can prepare according to the auxiliary agent preparation method that this area is conventional,
Can be with made into particulate form or microspheres form, preferably microsphere, it is simple to fluidisation.Preferably, described desulfurization
The mean diameter of auxiliary agent is 40-100 micron.
According to the present invention, described silica source can there is no particular limitation, under preferable case, and described oxygen
SiClx source can be the natural minerals that silicon oxide or silica content are more than 45 weight %.Preferably, institute
Stating silica source can be kieselguhr, expanded perlite, Kaolin, silicalite, hydrolysis oxidation silicon, big
At least one in hole silicon oxide and silica gel.
In the desulphurization catalyst that the method that the present invention provides prepares, the content of each component calculates according to inventory
Draw.
Oxide according at least one metal in the present invention, described IIB, VB and group vib is tool
There is the metal-oxide of storage sulfur performance, under preferable case, in described IIB, VB and group vib at least
The oxide of a kind of metal is the oxide of at least one metal in vanadium, zinc and molybdenum；It is preferably zinc oxide.
According to the present invention, at least one metal-oxide in described IVA race and Group IVB be have viscous
The binding agent of knot performance, at least one metal oxygen under preferable case, in described IVA race and Group IVB
Compound is at least one metal-oxide in titanium, zirconium and stannum.
According to the present invention, the preferred lanthanum of described rare earth oxide and/or cerium and/or the oxide of neodymium, the most excellent
Selecting described rare earth oxide is the oxide of one or more in lanthanum, cerium and neodymium.
A kind of method that present invention also offers sulfur-bearing hydrocarbon desulfurization, the method includes: anti-in sulfur-bearing hydrocarbon desulfurization
Under the conditions of Ying, in sulfur-bearing hydrocarbon desulfurization reactor, sulfur-bearing hydrocarbon be contacted with catalyst system with hydrogen donor,
Obtain desulfurization sulfur-bearing hydrocarbon and carry the desulfurizing assistant agent of sulfur；Wherein, described catalyst system provides for the present invention
Catalyst system, the ordered structure catalyst in described catalyst system is deposited with the form of beds
, the desulfurizing assistant agent in described catalyst system passes through beds with the form of fluidisation.
The present invention provide sulfur-bearing hydrocarbon desulfurization method in, ordered structure catalyst include ordered structure carrier and
Active component coating, has the parallel channels of both ends open, in active component coating in ordered structure carrier
It is distributed on the inwall in duct containing active metal.It is anti-that ordered structure catalyst may be used for sulfur-bearing hydrocarbon desulfurization
Answering as fixing beds in device, the sulfur-bearing hydrocarbon of flowing and hydrogen donor can flow by regular knot
Structure beds, i.e. can flow by distribution on the duct in ordered structure carrier, with cell walls
Active component coating reacts under sulfur-bearing hydrocarbon desulfurization reaction condition.Sulfur-bearing hydrocarbon desulfurization reactor can be
Conventional reactor, such as, can be fixed bed reactors etc., wherein uses fixed bed reactors as instead
When answering device, the catalyst system of the present invention is seated in fixed bed reactors, wherein, and described caltalyst
The desulfurization presented in beds, in described catalyst system of the ordered structure catalyst in system
Auxiliary agent passes through beds with the form of fluidisation.
Containing the metal-oxide with storage sulfur performance in desulfurizing assistant agent.Desulfurizing assistant agent is microsphere, Ke Yiliu
Change form flows in sulfur-bearing hydrocarbon desulfurization reactor, it is possible to mixes with sulfur-bearing hydrocarbon, hydrogen donor and flows logical
Cross the duct in ordered structure carrier, store the sulfide cracked out from sulfur-bearing hydrocarbon, become and carry the de-of sulfur
Sulfur auxiliary agent.The desulfurizing assistant agent carrying sulfur flowing out sulfur-bearing hydrocarbon desulfurization reactor can regenerate further, then
Sulfur-bearing hydrocarbon desulfurization can be reused for after life.In the method for the sulfur-bearing hydrocarbon desulfurization that the present invention provides, containing living
Property metal ordered structure catalyst only need to operate under sulfur-bearing hydrocarbon desulfurization reaction condition, and desulfurizing assistant agent need
To operate by alternate repetition under the conditions of sulfur-bearing hydrocarbon desulfurization reaction condition and regenerative response.So can keep away
Exempting from when active metal and desulfurizing assistant agent are prepared as one, active metal has to repeatedly experience oxidation regeneration
The situation of-reduction, and repeatedly experience oxidation regeneration-reduction and active metal can be made to assemble, reduce desulphurizing activated
And stability.
According to the present invention, described sulfur-bearing hydrocarbon desulfurization reaction condition can use sulfur-bearing commonly used in the art
The condition of hydrocarbon desulfurization reaction, it is also possible to combine the use of ordered structure catalyst, under preferable case, described
Sulfur-bearing hydrocarbon desulfurization reaction condition may include that reaction temperature is 200-550 DEG C, and reaction pressure is
0.5-5MPa, sulfur-bearing hydrocarbon charging weight (hourly) space velocity (WHSV) is 0.1-100h-1, hydrogen donor with the volume ratio of sulfur-bearing hydrocarbon is
0.01-1000, the desulfurizing assistant agent in described catalyst system is 0.1-10 with the weight ratio of sulfur-bearing hydrocarbon.Preferably
Reaction temperature is 300-500 DEG C, and reaction pressure is 1-3.5MPa, and sulfur-bearing hydrocarbon charging weight (hourly) space velocity (WHSV) is
1-10h-1, hydrogen donor is 0.05-500 with the volume ratio of sulfur-bearing hydrocarbon, and the desulfurization in described catalyst system helps
Agent is 0.5-5 with the weight ratio of sulfur-bearing hydrocarbon.Above-mentioned reaction condition can be more beneficial for sulfur-bearing hydrocarbon desulfurization reaction
Carry out, reduce the generation of unfavorable side reaction.
In the present invention, sulfur-bearing hydrocarbon charging weight (hourly) space velocity (WHSV) refers to the weight of the charging of sulfur-bearing hydrocarbon per hour and urges
The charge weitght ratio of the active component coating on ordered structure catalyst in agent system.
In the present invention, the desulfurizing assistant agent in described catalyst system refers to desulfurization with the weight ratio of sulfur-bearing hydrocarbon
The mass flow of auxiliary agent and the ratio of sulfur-bearing hydrocarbon feedstock quality flow.
According to the present invention, described desulfurizing assistant agent needs to regenerate, and sulfur performance is stored up in having of being contained
The sulfide abjection of absorption on metal-oxide, makes desulfurizing assistant agent can be reused for sulfur-bearing hydrocarbon desulfurization.Excellent
In the case of choosing, the method for the present invention also includes: under the conditions of regenerative response, in a regenerator by described load
The desulfurizing assistant agent of sulfur and rejuvenating gas contacts, obtain the desulfurizing assistant agent of regeneration.
According to the present invention, the regeneration that the condition for desulfurizing assistant agent regeneration can be commonly used in the art is anti-
Answer condition.Under preferable case, described regenerative response condition includes: regeneration temperature is 300-800 DEG C, then
Raw pressure is 0.1-3MPa, and regeneration gas feed volume air speed is 500-1500h-1, regeneration gas is for containing
Carrier of oxygen.Preferably regeneration temperature is 350-600 DEG C, and regeneration pressure is 0.1-1MPa, and regeneration gas feeds
Volume space velocity is 500-1000h-1.Regeneration gas can be at least one selected from oxygen, air, oxygen with
The gas of the mixture of the mixture of noble gas, air and noble gas.Above-mentioned condition can be preferably
Removing carries the sulfide of absorption on the desulfurizing assistant agent of sulfur.
According to the present invention, it is to carry out in high pressure hydrogen atmosphere that described desulfurizing assistant agent carries out sulfur-bearing hydrocarbon desulfurization reaction
, it is also in high pressure hydrogen gas from the desulfurizing assistant agent of the described load sulfur of sulfur-bearing hydrocarbon desulfurization reactor discharge
Atmosphere, and the desulfurizing assistant agent of described load sulfur carries out regenerating and carries out under low-pressure oxygen atmosphere, directly will be from
It is dangerous that the desulfurizing assistant agent of the described load sulfur that sulfur-bearing hydrocarbon desulfurization reactor is discharged carries out regenerating.Therefore, excellent
In the case of choosing, before the method for the present invention is additionally included in desulfurizing assistant agent and the rejuvenating gas contacts of described load sulfur,
The desulfurizing assistant agent of described load sulfur is carried out atmosphere displacement and decompression, makes the desulfurizing assistant agent of described load sulfur from high pressure
Hydrogen atmosphere enters as low pressure inert atmosphere.
According to the present invention, the desulfurizing assistant agent of the regeneration obtained from regenerator is added sulfur-bearing hydrocarbon desulfurization reaction
Device carries out sulfur-bearing hydrocarbon desulfurization reaction, needs the desulfurizing assistant agent making regeneration to be again in high pressure hydrogen atmosphere,
In the case of it is therefore preferable that, after the method is additionally included in desulfurizing assistant agent and the rejuvenating gas contacts of described load sulfur,
The desulfurizing assistant agent of described regeneration is carried out atmosphere displacement and pressurization, makes the desulfurizing assistant agent of described regeneration from low pressure
It is high pressure hydrogen atmosphere that oxygen atmosphere enters, and returns in described sulfur-bearing hydrocarbon desulfurization reactor.
In the case of according to the invention it is preferred to, the method is additionally included in sulfur-bearing hydrocarbon and hydrogen donor and catalyst
Before system contact, under the reducing conditions, by the ordered structure catalyst in described catalyst system and reduction
Gas contacts.The active metal in ordered structure catalyst can be made to exist with reduction-state form, be conducive to
The carrying out of sulfur-bearing hydrocarbon desulfurization reaction.
In the case of according to the invention it is preferred to, described reducing condition includes: temperature is 300-600 DEG C, pressure
Power is 0.2-5MPa, and reducing gas feed volume air speed is 500-1500h-1, reducing gas is hydrogen
Atmosphere；Preferably temperature is 300-450 DEG C, and pressure is 0.5-3.5MPa, reducing gas feed volume air speed
For 500-1000h-1.Hydrogen content 10-60 volume % in reducing gas.
According to the present invention, described sulfur-bearing hydrocarbon can be selected from natural gas, dry gas, liquefied gas, gasoline, kerosene,
One or more in diesel oil and gas oil, preferably gasoline and/or diesel oil.Above-mentioned gasoline, kerosene, bavin
Oil and gas oil fraction are its full fraction and/or its part narrow fraction.The sulfur content of described sulfur-bearing hydrocarbon is 50
More than micro-gram gram, preferably more than 100 micro-gram gram.The sulfur content of the most described sulfur-bearing hydrocarbon can be
The micro-gram gram of 100-1500.
According to the present invention, described hydrogen donor is selected from one or both in hydrogen, hydrogen-containing gas and hydrogen supply agent
Above mixture.Hydrogen refers to the hydrogen of various purity, hydrogen-containing gas preferred catalytic cracking (FCC)
One or more in dry gas, coking dry gas, thermal cracking dry gas.Hydrogen volume content is at 30 volume %
Above, at least one in naphthane, decahydronaphthalene and indane of hydrogen supply agent.
One according to the present invention is preferred embodiment, it is preferable that as it is shown in figure 1, the method for the present invention
The device of sulfur-bearing hydrocarbon desulfurization is carried out, this device include sulfur-bearing hydrocarbon desulfurization reactor 1, atmosphere displacement and
Voltage transformation unit and regenerator 25；The bottom of described sulfur-bearing hydrocarbon desulfurization reactor 1 is provided with sulfur-bearing hydrocarbon and confession
Hydrogen body feed pipe 5, desulfurizing assistant agent feed pipe 6, the top of described sulfur-bearing hydrocarbon desulfurization reactor 1 is provided with
Exhaustor 12 and discharge pipe 14；Described atmosphere displacement and voltage transformation unit on be provided with reactor receptor 15,
Reactor feed tank 31, Regenerator receiver 28, regenerator feed tank 22, displacement gas enter pipe (figure
In unmarked) and displacement gas discharge pipe 19, wherein, the displacement of described atmosphere and voltage transformation unit also include locking
Hopper 18；Described reactor receptor 15, described reactor feed tank 31, described Regenerator receiver
28 all connect with described locking hopper 18 with described regenerator feed tank 22；Set on described regenerator 25
It is equipped with spent agent feed pipe 23, regeneration gas air inlet pipe 24, smoke discharge pipe 26 and regenerative agent discharge pipe 27；
Wherein, described discharge pipe 14 connects with described reactor receptor 15, described regenerator feed tank 22
Connecting with described spent agent feed pipe 23, described regenerative agent discharge pipe 27 is with Regenerator receiver 28 even
Logical, described reactor feed tank 31 connects with desulfurizing assistant agent feed pipe 6, and described sulfur-bearing hydrocarbon desulfurization is reacted
Being filled with described catalyst system in device 1, the method includes:
Sulfur-bearing hydrocarbon bottom sulfur-bearing hydrocarbon desulfurization reactor 1 of sulfur-bearing hydrocarbon and hydrogen and hydrogen donor feed pipe 5 enter
Enter sulfur-bearing hydrocarbon desulfurization reactor 1 and the desulfurizing assistant agent desulfurizing assistant agent bottom sulfur-bearing hydrocarbon desulfurization reactor 1 to enter
Material pipe 6 enters sulfur-bearing hydrocarbon desulfurization reactor 1 and contacts with described catalyst system；Reacted product is through row
Trachea 12 is sent to follow-up product separation system；The desulfurizing assistant agent carrying sulfur is sent to reactor from discharge pipe 14
Receptor 15, is sent to locking hopper 18, at locking hopper 18 in reactor receptor 15 after stripping
The desulfurizing assistant agent of middle load sulfur is put by the noble gas (for example, nitrogen etc.) through being passed through from displacement gas entrance pipe
Enter low pressure inert atmosphere from hydrogen gas environment after changing and become desulfurizing assistant agent to be generated, the gas warp displaced
Displacement gas discharge pipe 19 is sent to combustion furnace and burns, and desulfurizing assistant agent to be generated is delivered to regenerator feed tank 22,
Entering regenerator 25 by spent agent feed pipe 23 again, oxygen-containing gas passes through regeneration gas air inlet pipe 24 simultaneously
Enter regenerator 25 from the bottom of regenerator 25, desulfurizing assistant agent to be generated and oxygen-containing gas are at regenerator 25
In and flow contact through burning sulfur, burning and discharge sulfur-containing smoke gas and regenerative sulfur binding auxiliary agent after carbon, sulfur-containing smoke gas is in regeneration
Device 25 top is delivered to sulfur system processed or alkali cleaning through smoke discharge pipe 26 after separating with regenerative sulfur binding auxiliary agent and takes off
Except SOx, regenerative sulfur binding auxiliary agent is transported to through regenerative agent discharge pipe 27 from regenerator 25 top emulsion zone again
In raw device receptor 28, after promoting with noble gas, it is delivered to locking hopper 18, at locking hopper 18
Middle regenerative sulfur binding auxiliary agent enters high pressure after being replaced by the hydrogen stripped being passed through from displacement gas entrance pipe and boost
Hydrogen environment, then be delivered in reactor feed tank 31, it is then sent to desulfurizing assistant agent feed pipe 6, then
Secondary entrance sulfur-bearing hydrocarbon desulfurization reactor 1, for sulfur-bearing hydrocarbon desulfurization, completes being carried out continuously of desulphurization reaction.
In the case of according to the invention it is preferred to, described sulfur-bearing hydrocarbon desulfurization reactor be fixed bed reactors such as
For monolithic reactors, described regenerator is fluid bed regenerator.
In the present invention, as it is shown in figure 1, described sulfur-bearing hydrocarbon desulfurization reactor can erect placement.Described contain
Sulfur hydrocarbon desulfurization reactor can have beds district, can place the catalysis of one or more ordered structure
Agent.The ordered structure catalyst 8 placed makes its internal duct be parallel in sulfur-bearing hydrocarbon desulfurization reactor
The both ends open of axis, i.e. duct can connect with top and the bottom of sulfur-bearing hydrocarbon desulfurization reactor respectively,
Thus form the passage that reaction mass can flow in sulfur-bearing hydrocarbon desulfurization reactor along the vertical direction, and
Active component coating containing active metal is distributed in these cell walls.Polylith ordered structure catalyst is permissible
It is positioned to multilamellar, and every layer can also have one or more.Have between every layer of ordered structure catalyst 8
Grid 9, is used for supporting ordered structure catalyst and can playing material distribution effect.Described sulfur-bearing hydrocarbon desulfurization
The height of reactor and the ratio of inside diameter can be 3-10:1.Described sulfur-bearing hydrocarbon desulfurization reactor is permissible
There is 1-5 layer ordered structure catalyst.Every layer can have 1-200 block ordered structure catalyst.
In the lower section of sulfur-bearing hydrocarbon desulfurization reactor and can there is sulfur-bearing hydrocarbon in the lower section of ordered structure catalyst 8
With hydrogen donor feed pipe 5, desulfurizing assistant agent feed pipe 6.In ordered structure catalyst 8 and sulfur-bearing hydrocarbon and confession
Distributor 7 can also be had between hydrogen body feed pipe 5, desulfurizing assistant agent feed pipe 6.
The device of the sulfur-bearing hydrocarbon desulfurization that the present invention provides can also have preheating before sulfur-bearing hydrocarbon desulfurization reactor
Device 3, is used for heating sulfur-bearing hydrocarbon and hydrogen supply agent.
Device can be responded above sulfur-bearing hydrocarbon desulfurization reactor and above ordered structure catalyst
Expanding reach 10, wherein has cyclone separator 11.Cyclone separator has charging aperture 13, reaction gas outlet
12 and dipleg.Charging aperture 13 on rotation point separator is for receiving reacting gas product and carrying the desulfurization of sulfur
Auxiliary agent.The exhaustor that reaction gas outlet can be arranged with the top of sulfur-bearing hydrocarbon desulfurization reactor is same
Arrange, discharge for reacting gas product.Dipleg can be with the top setting of sulfur-bearing hydrocarbon desulfurization reactor
Discharge pipe is same setting, for the desulfurizing assistant agent carrying sulfur is discharged to atmosphere displacement and voltage transformation unit.Institute
The inside diameter stating reactor expanding reach 10 is permissible with the inside diameter ratio of described sulfur-bearing hydrocarbon desulfurization reactor
For 1.5-3:1.
In the present invention, described regenerator can be fluid bed regenerator commonly used in the art, at this not
Repeat again.
Device schematic diagram below in conjunction with the sulfur-bearing hydrocarbon desulfurization shown in Fig. 1 describes the operation of sulfur-bearing hydrocarbon desulfurization
Journey.
Reduction process: hydrogen enters preheater 3 through the first pipeline 2, through the second pipeline 4 from containing after preheating
Sulfur-bearing hydrocarbon and hydrogen donor feed pipe 5 bottom sulfur hydrocarbon desulfurization reactor 1 enter ordered structure catalyst, also
Gas after former is discharged from exhaustor 12.Terminate reduction process.
Sweetening process: sulfur-bearing hydrocarbon and hydrogen enter preheater 3 through the first pipeline 2, through the second pipe after preheating
The line 4 sulfur-bearing hydrocarbon bottom sulfur-bearing hydrocarbon desulfurization reactor 1 and hydrogen donor feed pipe 5 enter sulfur-bearing hydrocarbon desulfurization
Reactor 1.Desulfurizing assistant agent desulfurizing assistant agent feed pipe 6 bottom sulfur-bearing hydrocarbon desulfurization reactor 1 enters and contains
Sulfur hydrocarbon desulfurization reactor 1.Sulfur-bearing hydrocarbon, hydrogen and desulfurizing assistant agent mix after distributor 7 commonly through rule
Whole structure catalyst 8 and grid 9, discharge above ordered structure catalyst 8 reacted product and
The desulfurizing assistant agent carrying sulfur enters reactor expanding reach 10.The most reacted product and the desulfurizing assistant agent of load sulfur
Another charging aperture 13 risen on entrance cyclone separator 11.Reacted product is after exhaustor 12 is sent to
Continuous product separation system.The desulfurizing assistant agent carrying sulfur is sent to reactor receptor 15 from discharge pipe 14,
Reactor receptor 15 is sent to locking material through the 3rd pipeline 16 and the 4th pipeline 17 after stripping successively
Bucket 18.The desulfurizing assistant agent of sulfur is carried by through entering, from displacement gas, the indifferent gas that pipe is passed through in locking hopper 18
Enter low pressure inert atmosphere from hydrogen gas environment after body displacement and become desulfurizing assistant agent to be generated, the gas displaced
Body is sent to combustion furnace through displacement gas discharge pipe 19 and burns.Desulfurizing assistant agent to be generated is through the 5th pipeline 20 and the 6th
Pipeline 21 is delivered to regenerator feed tank 22, then enters regenerator 25 by spent agent feed pipe 23.
Oxygen-containing gas (regeneration gas) is entered from the bottom of regenerator 25 by regeneration gas air inlet pipe 24 again simultaneously
Raw device 25.Desulfurizing assistant agent to be generated and oxygen-containing gas are in regenerator 25 and flow and contact after burning sulfur, burning carbon
Discharge sulfur-containing smoke gas and regenerative sulfur binding auxiliary agent.Sulfur-containing smoke gas is at regenerator 25 top and regenerative sulfur binding auxiliary agent
It is delivered to sulfur system processed or alkali cleaning removing SO through smoke discharge pipe 26 after separationx.Regenerative sulfur binding auxiliary agent from
Regenerator 25 top emulsion zone is in regenerative agent discharge pipe 27 is transported to Regenerator receiver 28, with lazy
It is delivered to locking hopper 18 through the 7th pipeline 29 and the 4th pipeline 17 after property gas lift.At locking hopper
In 18, regenerative sulfur binding auxiliary agent enters height after being replaced by the hydrogen stripped being passed through from displacement gas entrance pipe and boost
Pressure hydrogen environment, then be delivered in reactor feed tank 31 through the 5th pipeline 20 and the 8th pipeline 30,
Then it is delivered to desulfurizing assistant agent feed pipe 6 by the 9th pipeline 32, sulfur-bearing hydrocarbon desulfurization can be again introduced into anti-
Answer device 1, for sulfur-bearing hydrocarbon desulfurization, complete being carried out continuously of desulphurization reaction.
In the present invention, the pressure related to all represents with gauge pressure.
Hereinafter will be described the present invention by embodiment.
Sulfur content in following example and comparative example passes through off-line chromatogram analysis method, uses An Jielun public
The GC6890-SCD instrument of department is measured.
Use GB/T 503-1995 and GB/T 5487-1995 measure reaction raw materials catalytically cracked gasoline and
The motor octane number (MON) of desulphurization catalyst stably rear product gasoline and research octane number (RON)
(RON)。
Embodiment 1
The present embodiment is for illustrating catalyst system and the method for sulfur-bearing hydrocarbon desulfurization of the present invention.
(1) catalyst system (weight of the active component coating of desulfurizing assistant agent and ordered structure catalyst
Ratio is 1:1).
Prepared by ordered structure catalyst: by Ni/Al2O3For active component coating, it is coated in cordierite honeycomb
Obtain ordered structure on carrier (carrier hole density is 400 holes/square inch, and percent opening is 70%) to urge
Agent, on active component coating, nickel content is 80 weight %, Al2O3Content is 20 weight %.Catalyst
Middle active component coating content is 25 weight %.
Desulfurizing assistant agent uses following methods to prepare:
By 6.07 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, containing butt 6.0 kilograms), 0.32 thousand
Gram lanthana (traditional Chinese medicines group produces, containing butt 0.3 kilogram) and 8.5 kilograms of deionized waters mix, and stir
Zinc oxide serosity is obtained after mixing 30 minutes.
Take stannum oxide 1.60 kilograms (Tianjin Bath steps chemical industry and produces, containing butt 1.20 kilograms) and 3.0
Kilogram Kaolin (containing butt 2.50 kilograms) (deriving from Qilu Petrochemical catalyst plant) under agitation mix,
After being subsequently adding 3.6 kilograms of mix homogeneously of deionized water, the hydrochloric acid adding 300 milliliter of 30 weight % (is changed
Learn pure, Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours, add
After the mixing of zinc oxide serosity, stirring obtains auxiliary agent serosity in 1 hour.
Above-mentioned auxiliary agent serosity uses Niro Bowen Nozzle TowerTMThe spray dryer of model is carried out
Being spray-dried, being spray-dried pressure is 8.5 to 9.5MPa, inlet temperature less than 500 DEG C, outlet temperature
It is about 150 DEG C.The microsphere obtained by spray drying is first dried 1 hour at 150 DEG C, then 480
At DEG C, roasting obtains desulfurizing assistant agent (mean diameter 30 microns) for 1 hour.Consisting of of auxiliary agent: zinc oxide
60.0 weight %, lanthana 3.0 weight %, stannum oxide 12.0 weight %, Kaolin 25.0 weight %.
(2) sulfur-bearing hydrocarbon desulfurization.
Reduction: by ordered structure catalyst 450 DEG C, under 1.4MPa, with containing 96 volume % hydrogen
Gas reduction 2 hours, reducing gas feed volume air speed is 1000h-1。
Desulfurization: use the device shown in Fig. 1 and flow process, with hydrogen as hydrogen medium, in temperature 400
DEG C, pressure 1.4MPa, gasoline weight (hourly) space velocity (WHSV) be 5h-1, hydrogen is 45 with gasoline-volume ratio, and desulfurization helps
Gasoline, with under the sulfur-bearing hydrocarbon desulfurization reaction condition that weight ratio is 2 of sulfur-bearing hydrocarbon, is carried out desulphurization reaction by agent,
Gasoline composition is shown in Table 1.Reaction condition and reaction result are shown in Table 2.
Embodiment 2
The present embodiment is for illustrating catalyst system and the method for sulfur-bearing hydrocarbon desulfurization of the present invention.
According to the method for embodiment 1, except for the difference that, the reduction in (2): with " 400 DEG C " with " contain
70 volume % hydrogen ", substitute " 450 DEG C " and " containing 96 volume % hydrogen "；Desulfurization: by " temperature 430
DEG C, pressure 3.0MPa, gasoline weight (hourly) space velocity (WHSV) be 7h-1, hydrogen and gasoline-volume ratio 100 ", substitute " temperature
Spend 400 DEG C, pressure 1.4MPa, gasoline weight (hourly) space velocity (WHSV) be 5h-1, hydrogen is 45 with gasoline-volume ratio ".
Reaction condition and reaction result are shown in Table 2.
Embodiment 3
The present embodiment is for illustrating catalyst system and the method for sulfur-bearing hydrocarbon desulfurization of the present invention.
According to the method for embodiment 1, except for the difference that, the reduction in (2): with " 500 DEG C " with " contain
70 volume % hydrogen ", substitute " 400 DEG C " and " hydrogen "；Desulfurization: with " gasoline weight (hourly) space velocity (WHSV) is 12h-1",
" gasoline weight (hourly) space velocity (WHSV) is 5h to replacement-1”.Reaction condition and reaction result are shown in Table 2.
Embodiment 4
Prepare the catalyst system of the present invention as described in Example 1.Difference is:
(1) catalyst system (weight of the active component coating of desulfurizing assistant agent and ordered structure catalyst
Ratio is 9:1).
Prepared by ordered structure catalyst: by Ni/Al2O3For active component coating, it is coated in cordierite honeycomb
Obtain ordered structure on carrier (carrier hole density is 400 holes/square inch, and percent opening is 70%) to urge
Agent, on active component coating, nickel content is 30 weight %, Al2O3Content is 70 weight %.Catalyst
Middle active component coating content is 30 weight %.
Desulfurizing assistant agent uses following methods to prepare:
By 3.04 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, containing butt 3.0 kilograms), 0.11 thousand
Gram cerium oxide (traditional Chinese medicines group produces, containing butt 0.1 kilogram) and 4.5 kilograms of deionized waters mix, and stir
Zinc oxide serosity is obtained after mixing 30 minutes.
The titanium tetrachloride (Beijing Chemical Plant, analytical pure) of 8.24kg is slowly added into going of 10.88kg
In ionized water, and it is slowly stirred and avoids titanium oxide crystal to separate out, obtain the titanium colloidal sol of pale yellow transparent,
PH=1.0；Take the Kaolin (containing butt 3.50 kilograms) (deriving from Qilu Petrochemical catalyst plant) of 4.2 kilograms
After adding 8.0 kilograms of mix homogeneously of deionized water, add after mixing 1 hour with the stirring of above-mentioned titanium colloidal sol
After the mixing of zinc oxide serosity, stirring obtains auxiliary agent serosity in 1 hour.
Above-mentioned auxiliary agent serosity uses Niro Bowen Nozzle TowerTMThe spray dryer of model is carried out
Being spray-dried, being spray-dried pressure is 8.5 to 9.5MPa, inlet temperature less than 500 DEG C, outlet temperature
It is about 150 DEG C.The microsphere obtained by spray drying is first dried 1 hour at 150 DEG C, then 480
At DEG C, roasting obtains desulfurizing assistant agent (mean diameter 65 microns) for 1 hour.Consisting of of auxiliary agent: zinc oxide
30.0 weight %, cerium oxide 1.0 weight %, titanium oxide 34.0 weight %, Kaolin 35.0 weight %.
Reaction condition is with embodiment 1, and reaction result is shown in Table 2.
Embodiment 5
Prepare the catalyst system of the present invention as described in Example 1.Difference is:
(1) catalyst system (weight of the active component coating of desulfurizing assistant agent and ordered structure catalyst
Ratio is 5:1).
Prepared by ordered structure catalyst: by Ni/Al2O3For active component coating, it is coated in cordierite honeycomb
Obtain ordered structure on carrier (carrier hole density is 400 holes/square inch, and percent opening is 70%) to urge
Agent, on active component coating, nickel content is 60 weight %, Al2O3Content is 40 weight %.Catalyst
Middle active component coating content is 20 weight %.
Desulfurizing assistant agent uses following methods to prepare:
By 7.6 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, containing butt 7.5 kilograms), 1.1 kilograms
Cerium oxide (traditional Chinese medicines group produces, containing butt 1.0 kilograms) and 10 kilograms of deionized water mixing, stirring
Zinc oxide serosity is obtained after 30 minutes.
The Zirconium tetrachloride. (Beijing Chemical Plant, analytical pure) of 0.95kg is slowly added into the dense of 1.29kg
Spend and the salpeter solution of 5 weight % makes pH=2.0, and be slowly stirred and avoid crystal of zirconium oxide to separate out, obtain
Water white zirconium colloidal sol；The Kaolin (containing butt 1.0 kilograms) taking 1.2 kilograms (derives from Qilu Petrochemical
Catalyst plant) add after 1.0 kilograms of mix homogeneously of deionized water, under agitation mix with above-mentioned zirconium colloidal sol
0.5 hour, after being subsequently adding the mixing of zinc oxide serosity, stirring obtained auxiliary agent serosity in 1 hour.
Above-mentioned auxiliary agent serosity uses Niro Bowen Nozzle TowerTMThe spray dryer of model is carried out
Being spray-dried, being spray-dried pressure is 8.5 to 9.5MPa, inlet temperature less than 500 DEG C, outlet temperature
It is about 150 DEG C.The microsphere obtained by spray drying is first dried 1 hour at 150 DEG C, then 480
At DEG C, roasting obtains desulfurizing assistant agent (mean diameter 165 microns) for 1 hour.Consisting of of auxiliary agent: oxidation
Zinc 75.0 weight %, cerium oxide 10 weight %, zirconium oxide 5.0 weight %, Kaolin 10.0 weight %.
Reaction condition is with embodiment 1, and reaction result is shown in Table 2.
Comparative example 1
Forth generation industrially desulfurized adsorbent (its produced with Switzerland's Clariant Corporation (former South Chemical Company)
In, catalyst is with zinc oxide, Silicon stone and aluminium oxide as carrier, and Ni is as accelerator in load；Consist of:
(Ni 15.7 weight %, ZnO 52.7 weight %, Al2O316.8 weight %, SiO214.8 weight %) adopt
Gasoline desulphurization reaction is carried out with fluidized-bed reactor.
Desulphurization reaction condition is；With hydrogen as hydrogen medium, temperature is 400 DEG C, and pressure is 1.4MPa,
Gasoline weight (hourly) space velocity (WHSV) is 5h-1, hydrogen is 45 with gasoline-volume ratio.
Gasoline composition is shown in Table 1, and concrete reaction condition and reaction result are shown in Table 2.
Table 1
| Project | Analytical data | Project | Analytical data |
| Density (20 DEG C)/kg.m-3 | 727.3 | Induction period/min | 922 |
| Existent gum/mg. (mL)-1 | 0.34 | Boiling range/DEG C | |
| Refraction index (20 DEG C) | 1.4143 | Initial boiling point | 38.5 |
| Sulfur content/ng. (μ L)-1 | 960.48 | 5% | 49.0 |
| Mercaptan sulfur content/ng. (μ L)-1 | 10.2 | 10% | 55.5 |
| Hydrogen sulfide content/ng. (μ L)-1 | 0 | 30% | 74.7 |
| Octane number (RON/MON) | 93.7/83.6 | 50% | 97.2 |
| Race's composition stops long-pending/% | 70% | 124.2 | |
| Saturated hydrocarbons | 44.0 | 90% | 155.2 |
| Alkene | 41.2 | 95% | 165.2 |
| Aromatic hydrocarbons | 14.8 | The end point of distillation | 185.0 |
Table 2
Note:
1, the sulfur content of feed gasoline be 960ppm, RON be 93.7, MON is 83.6.
2, △ MON represents the value added of product MON；
3, △ RON represents the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
Being shown by table 2 result, in embodiment 1, product sulfur content is less than 0.5ppm in initial reaction stage
(chromatographic detectability), along with the carrying out in response time, in product, sulfur content gradually rises, but instead
At the end of Ying, product sulfur content also only has 8.9ppm, and loss of octane number averagely only has 0.22 unit.
In embodiment 2, due to reaction pressure and the raising of reaction temperature, product sulfur content is in reaction
At the end of only 1.9ppm, and loss of octane number averagely only has 0.23 unit.Although reaction pressure and
Being significantly increased of reaction hydrogen-oil ratio is likely to result in anti-knock index loss increasing, but owing to improve simultaneously
Reaction temperature, it is suppressed that the carrying out of hydrogenation reaction, the cracking ability of catalyst strengthens simultaneously, small molecule hydrocarbon
Class increases, and therefore the loss of octane number of product the most only reduces 0.23 unit, and bulk product liquid is received still
It is maintained at 99.7%.
In embodiment 3, owing on ordered structure catalyst, the reducing degree of promoter metals increases, activity
Tenor increases, and makes the most also to have higher desulphurizing activated.Because weight (hourly) space velocity (WHSV) increases
Adding, the response time of sulfur-bearing hydrocarbon shortens, and reduces the cracking reaction degree of depth and the green coke amount of sulfur-bearing hydrocarbon, catalysis
Agent deactivation rate slows down.Product sulfur content is only 4.7ppm at the end of reaction, and anti-knock index damages
Lose only 0.16 unit.Bulk product liquid is received and is maintained at 99.9%.
Although when in comparative example 1, reaction starts, in product, sulfur content is relatively low, only 2.6ppm, but
Along with the carrying out of reaction, in product, sulfur content is increased to 49.2ppm, far above the 1.9ppm of embodiment 2,
Illustrate on the fluidized-bed reactor in single reaction district, desulphurizing activated meeting the carrying along with sulfur load capacity of adsorbent
High and rapid decrease.
As can be seen here, the catalyst system that the present invention provides can have the most desulphurizing activated and desulfurization stable
Property.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (21)
1. a catalyst system for sulfur-bearing hydrocarbon desulfurization, this catalyst system includes desulfurizing assistant agent and regular
Structure catalyst；Described ordered structure catalyst include ordered structure carrier and be distributed in carrier inner surface and
/ or the active component coating of outer surface, on the basis of the gross weight of described active component coating, described activity
Component coating contains active metal and the substrate of 10-70 weight % of 30-90 weight %, described activity gold
Belong to for VIIB race and/or the metal of VIII；On the basis of the gross weight of described desulfurizing assistant agent, described de-
Sulfur auxiliary agent contains at least one metal-oxide in the Group IVB of 5-35 weight % and IVA race, 0.5-10
Weight % rare earth oxide, the silica source of 5-35 weight % and IIB, VB of 30-89.5 weight % and
The oxide of at least one metal in group vib, described desulfurizing assistant agent is mean diameter 20-200 micron
Microsphere；Described desulfurizing assistant agent with the weight ratio of the active component coating of described ordered structure catalyst is
1-9:1.
Catalyst system the most according to claim 1, wherein, with described ordered structure catalyst
Gross weight on the basis of, the content of described active component coating is 3-30 weight %.
Catalyst system the most according to claim 1, wherein, described ordered structure carrier is selected from
There is the monolithic substrate of the parallel channels structure of both ends open.
Catalyst system the most according to claim 3, wherein, the Kong Mi in the cross section of described carrier
Degree is 20-900 hole/square inch, and the percent opening in the cross section of described carrier is 20-80%.
5. according to the catalyst system described in any one in claim 1-4, wherein, described regular
Structure carrier is selected from cordierite honeycomb carrier, mullite honeycomb substrate, diamond honeycomb substrate, corundum honeybee
In nest carrier, fused alumina zirconia honeycomb substrate, quartz honeycomb substrate, nepheline honeycomb substrate and Anhydrite honeycomb substrate
At least one.
Catalyst system the most according to claim 1, wherein, described active metal be cobalt, nickel,
At least one in ferrum and manganese.
Catalyst system the most according to claim 1, wherein, described substrate selected from aluminium oxide,
In silicon oxide, amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide at least
A kind of.
Catalyst system the most according to claim 1, wherein, in described Group IVB and IVA race
At least one metal-oxide be the oxide of at least one metal in titanium, zirconium and stannum；Described rare earth oxygen
Compound is the oxide of one or more in lanthanum, cerium and neodymium.
Catalyst system the most according to claim 1, wherein, described silica source is silicon oxide
Or silica content is more than the natural minerals of 45 weight %.
Catalyst system the most according to claim 9, wherein, described silica source be kieselguhr,
In expanded perlite, Kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel at least one
Kind.
11. catalyst systems according to claim 1, wherein, described IIB, VB and VIB
The oxide of at least one metal in race is the oxide of at least one metal in vanadium, zinc and molybdenum.
The method of 12. 1 kinds of sulfur-bearing hydrocarbon desulfurizations, the method includes: under sulfur-bearing hydrocarbon desulfurization reaction condition,
In sulfur-bearing hydrocarbon desulfurization reactor, sulfur-bearing hydrocarbon is contacted with catalyst system with hydrogen donor；
Wherein, described catalyst system is the catalyst system in claim 1-11 described in any one,
Ordered structure catalyst in described catalyst system presented in beds, described catalyst
Desulfurizing assistant agent in system passes through beds with the form of fluidisation.
13. methods according to claim 12, wherein, described sulfur-bearing hydrocarbon desulfurization reaction condition bag
Including: reaction temperature is 200-550 DEG C, reaction pressure is 0.5-5MPa, and sulfur-bearing hydrocarbon charging weight (hourly) space velocity (WHSV) is
0.1-100h-1, hydrogen donor is 0.01-1000 with the volume ratio of sulfur-bearing hydrocarbon, taking off in described catalyst system
Sulfur auxiliary agent is 0.1-10 with the weight ratio of sulfur-bearing hydrocarbon.
14. methods according to claim 12, wherein, the method also includes: at regenerative response
Under the conditions of, in a regenerator by the desulfurizing assistant agent carrying sulfur obtained after haptoreaction and rejuvenating gas contacts,
Obtain the desulfurizing assistant agent of regeneration.
15. methods according to claim 14, wherein, described regenerative response condition includes: again
Raw temperature is 300-800 DEG C, and regeneration pressure is 0.1-3MPa, and regeneration gas feed volume air speed is
500-1500h-1, regeneration gas is oxygen-containing gas.
16. according to the method described in claims 14 or 15, and wherein, the method also includes: carrying sulfur
Desulfurizing assistant agent and rejuvenating gas contacts before, the desulfurizing assistant agent of described load sulfur is carried out atmosphere displacement and subtracts
Pressure, makes the desulfurizing assistant agent of described load sulfur enter low pressure inert atmosphere from high pressure hydrogen atmosphere.
17. according to the method described in claims 14 or 15, and wherein, the method also includes: carrying sulfur
Desulfurizing assistant agent and rejuvenating gas contacts after, the desulfurizing assistant agent of described regeneration is carried out atmosphere displacement and adds
Pressure, makes the desulfurizing assistant agent of described regeneration enter high pressure hydrogen atmosphere from low-pressure oxygen atmosphere, and returns described
In sulfur-bearing hydrocarbon desulfurization reactor.
18. methods according to claim 12, wherein, the method also includes: by sulfur-bearing hydrocarbon
Before contacting with catalyst system with hydrogen donor, under the reducing conditions, regular by described catalyst system
Structure catalyst contacts with reducing gas.
19. methods according to claim 18, wherein, described reducing condition includes: temperature is
300-600 DEG C, pressure is 0.2-5MPa, and reducing gas feed volume air speed is 500-1500h-1, reduction
Gas is hydrogeneous atmosphere.
20. methods according to claim 12, wherein, the method is at the device of sulfur-bearing hydrocarbon desulfurization
In carry out, this device includes the displacement of sulfur-bearing hydrocarbon desulfurization reactor (1), atmosphere and voltage transformation unit and regeneration
Device (25)；The bottom of described sulfur-bearing hydrocarbon desulfurization reactor (1) is provided with sulfur-bearing hydrocarbon and hydrogen donor feed pipe
(5), desulfurizing assistant agent feed pipe (6), the top of described sulfur-bearing hydrocarbon desulfurization reactor (1) is provided with row
Trachea (12) and discharge pipe (14)；It is provided with reactor in the displacement of described atmosphere and voltage transformation unit to receive
Device (15), reactor feed tank (31), Regenerator receiver (28), regenerator feed tank (22),
Displacement gas enters pipe and displacement gas discharge pipe (19), and wherein, the displacement of described atmosphere and voltage transformation unit are also wrapped
Include locking hopper (18)；Described reactor receptor (15), described reactor feed tank (31), institute
State Regenerator receiver (28) and described regenerator feed tank (22) all with described locking hopper (18)
Connection；Be provided with on described regenerator (25) spent agent feed pipe (23), regeneration gas air inlet pipe (24),
Smoke discharge pipe (26) and regenerative agent discharge pipe (27)；Wherein, described discharge pipe (14) is with described
Reactor receptor (15) connects, described regenerator feed tank (22) and described spent agent feed pipe (23)
Connection, described regenerative agent discharge pipe (27) connects with Regenerator receiver (28), and described reactor enters
Batch can (31) connects with desulfurizing assistant agent feed pipe (6), dress in described sulfur-bearing hydrocarbon desulfurization reactor (1)
Being filled with described catalyst system, the method includes:
Sulfur-bearing hydrocarbon from sulfur-bearing hydrocarbon desulfurization reactor (1) bottom of sulfur-bearing hydrocarbon and hydrogen and hydrogen donor feed pipe
(5) sulfur-bearing hydrocarbon desulfurization reactor (1) and desulfurizing assistant agent are entered from sulfur-bearing hydrocarbon desulfurization reactor (1) end
The desulfurizing assistant agent feed pipe (6) in portion enters sulfur-bearing hydrocarbon desulfurization reactor (1) and connects with described catalyst system
Touch；Reacted product is sent to follow-up product separation system through exhaustor (12)；The desulfurization carrying sulfur helps
Agent is sent to reactor receptor (15) from discharge pipe (14), through vapour in reactor receptor (15)
It is sent to locking hopper (18) after carrying, locking hopper (18) carries the desulfurizing assistant agent of sulfur by through from displacement
Become from hydrogen gas environment entrance low pressure inert atmosphere after the inert gas replacement that gas entrance pipe is passed through and treat
Raw desulfurizing assistant agent, the gas displaced is sent to combustion furnace through displacement gas discharge pipe (19) and burns, to be generated de-
Sulfur auxiliary agent is delivered to regenerator feed tank (22), then enters regenerator by spent agent feed pipe (23)
(25), oxygen-containing gas is entered from the bottom of regenerator (25) by regeneration gas air inlet pipe (24) simultaneously
Regenerator (25), desulfurizing assistant agent to be generated and oxygen-containing gas in regenerator (25) and flow contact through burn sulfur,
Discharging sulfur-containing smoke gas and regenerative sulfur binding auxiliary agent after burning carbon, sulfur-containing smoke gas is in regenerator (25) top and regeneration
Desulfurizing assistant agent is delivered to sulfur system processed or alkali cleaning removing SO through smoke discharge pipe (26) after separatingx, regeneration
Desulfurizing assistant agent is transported to regenerator from regenerator (25) top emulsion zone through regenerative agent discharge pipe (27) and connects
Receive in device (28), after promoting with noble gas, be delivered to locking hopper (18), in locking hopper (18)
Middle regenerative sulfur binding auxiliary agent enters high pressure after being replaced by the hydrogen stripped being passed through from displacement gas entrance pipe and boost
Hydrogen environment, then be delivered in reactor feed tank (31), it is then sent to desulfurizing assistant agent feed pipe (6),
It is again introduced into sulfur-bearing hydrocarbon desulfurization reactor (1), for sulfur-bearing hydrocarbon desulfurization, completes entering continuously of desulphurization reaction
OK.
21. methods according to claim 20, wherein, described sulfur-bearing hydrocarbon desulfurization reactor is rule
Whole structural response device, described regenerator is fluid bed regenerator.
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| CN108525660A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | A kind of method of sulfur-bearing hydrocarbon oxygenation desulfurization |
| CN111085187A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Regular carrier catalyst with desulfurization effect and preparation and application thereof |
| CN113144892A (en) * | 2021-05-26 | 2021-07-23 | 广州大学 | Air processor |
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| CN108404952B (en) * | 2017-02-10 | 2020-08-18 | 中国石油化工股份有限公司 | Desulfurization catalyst with regular structure, preparation method thereof and sulfur-containing hydrocarbon desulfurization method |
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| US6274533B1 (en) * | 1999-12-14 | 2001-08-14 | Phillips Petroleum Company | Desulfurization process and novel bimetallic sorbent systems for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108525660A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | A kind of method of sulfur-bearing hydrocarbon oxygenation desulfurization |
| CN111085187A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Regular carrier catalyst with desulfurization effect and preparation and application thereof |
| CN113144892A (en) * | 2021-05-26 | 2021-07-23 | 广州大学 | Air processor |
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