CN106140257A

CN106140257A - The catalyst system of sulfur-bearing hydrocarbon desulfurization and the method for sulfur-bearing hydrocarbon desulfurization

Info

Publication number: CN106140257A
Application number: CN201510209443.6A
Authority: CN
Inventors: 孙言; 田辉平; 王鹏; 林伟; 许明德; 徐志成
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-04-28
Filing date: 2015-04-28
Publication date: 2016-11-23
Anticipated expiration: 2035-04-28
Also published as: CN106140257B

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 transition metal promoter and the substrate of 10-70 weight % of 30-90 weight %；Described substrate contains the silica binder of at least one in the BEA structure of 70-90 weight % and the molecular sieve of FAU structure and 10-30 weight %；Described desulfurizing assistant agent contains the oxide of at least one metal in the aluminium oxide of 5-40 weight %, 5-40 weight % silica source and IIB, VB of 30-90 weight % and 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

The catalyst system of sulfur-bearing hydrocarbon desulfurization and the method for sulfur-bearing hydrocarbon desulfurization

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 contain 30-90 weight % transition metal promoter and The substrate of 10-70 weight %, described transition metal promoter is the metal of VIIB race and/or VIII； Described substrate contains at least one in the BEA structure of 70-90 weight % and the molecular sieve of FAU structure Silica binder with 10-30 weight %；On the basis of the gross weight of described desulfurizing assistant agent, described de- Sulfur auxiliary agent contains the aluminium oxide of 5-40 weight %, the silica source of 5-40 weight % and 30-90 weight % The oxide of at least one metal in IIB, VB and group vib, described desulfurizing assistant agent is mean diameter The microsphere of 20-200 micron；The active component coating of described desulfurizing assistant agent and described ordered structure catalyst Weight ratio 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 Transition metal promoter dispersion is higher, contacts easily with desulfurizing assistant agent, beneficially catalyst and auxiliary agent Synergism plays；

(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) employing has BEA or FAU molecular sieve promotion linear alkene and isomerization of paraffins and splits Change, improve the octane number of product gasoline.

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 transition metal promoter and the base of 10-70 weight % of 30-90 weight % Matter, described transition metal promoter is the metal of VIIB race and/or VIII；Described substrate contains 70-90 At least one in the BEA structure of weight % and the molecular sieve of FAU structure and the oxygen of 10-30 weight % SiClx binding agent；On the basis of the gross weight of described desulfurizing assistant agent, described desulfurizing assistant agent contains 5-40 weight The amount aluminium oxide of %, the silica source of 5-40 weight % and IIB, VB of 30-90 weight % and group vib In the oxide of at least one metal, 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, excellent Elect 2-5:1 as, for example, 2:1,3:1 or 5:1.

According to the present invention, described ordered structure catalyst contains can make the organic sulfur conversion in sulfur-bearing hydrocarbon be The transition metal promoter of hydrogen sulfide.Described transition metal promoter is made into active component coating form and divides Cloth is on ordered structure carrier.Described active component coating is distributed in the amount on ordered structure carrier can not had There is particularly restriction, under preferable case, on the basis of the gross weight of described ordered structure catalyst, described The content of active component coating 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 in the cross 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 transition metal promoter.Preferably, On the basis of the gross weight of described active component coating, described active component coating contains 40-80 weight % Transition metal promoter and the substrate of 20-60 weight %, substrate contain 70-85 weight % BEA knot At least one in the molecular sieve of structure and FAU structure and the silica binder of 15-30 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 Transition metal promoter is introduced in substrate.The method of well known to a person skilled in the art can be used, such as, soak Stain normal direction substrate introduces transition metal promoter, obtains catalyst.Can be with containing transition metal promoter Substrate described in the solution of compound or suspension impregnation.Described transition metal promoter compound is can be in roasting Be changed into the material of transition metal promoter oxide under the conditions of burning, transition metal promoter oxide under The reduction treatment that literary composition describes is reduced into as transition metal promoter.Described transition metal promoter chemical combination Thing can be selected from the acetate of transition metal promoter, carbonate, nitrate, sulfate, rhodanate And oxide, and two of which or two or more mixture etc..The concrete operations condition of infusion process and Method is the most known to those skilled in the art, does not repeats them here；(3) by the catalyst obtained with contain Aqueous solvent grinds to form serosity, and slurry solid content can be 20-40 weight %, i.e. obtains described catalyst slurry Liquid, this catalyst slurry contains transition metal promoter compound；(4) pass through with above-mentioned catalyst slurry Cladding process coats described ordered structure carrier and makes.Described cladding process can be water coating, infusion process or spray Pouring method.The concrete operations of coating are referred to the method described in CN 1199733C and carry out.By coating well The ordered structure carrier of described catalyst slurry is dried and roasting, i.e. can obtain being distributed in ordered structure Active component coating precursor on carrier.The condition being dried includes: temperature is 90-130 DEG C, and the time is 3-10 hour, more preferably temperature was 110-120 DEG C, and the time is 5-7 hour.The condition of roasting includes: Temperature 450-650 DEG C, the time is 8-20 hour.Containing transition metal in described active component coating precursor Accelerator 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 Transition metal promoter is introduced on body.Can be with the solution containing transition metal promoter compound or suspension Dipping is containing the ordered structure carrier of matrix coating and is dried and roasting, i.e. can obtain being distributed in regular Active component coating precursor on structure carrier, promotees containing transition metal in described active component coating precursor Enter agent oxide.The condition being dried includes: temperature is 90-130 DEG C, and the time is 3-10 hour, more excellent Selecting temperature to be 110-120 DEG C, the time is 5-7 hour.The condition of roasting includes: temperature 450-650 DEG C, Time is 8-20 hour.Described transition metal promoter compound is can be changed under roasting condition The material of transition metal promoter oxide, the reduction that transition metal promoter oxide will describe below Reduction is become transition metal promoter by process.Described transition metal promoter compound is selected from transition The acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide, and Two of which or two or more mixture etc..The concrete operations condition of infusion process and method have been this area Well known to technical staff, do not repeat them here.

According to the present invention, described active component coating can be by reducing active component coating precursor Processing, the transition metal promoter oxide contained by active component coating precursor is changed into transition metal and promotees Enter agent and prepare.Described reduction treatment can be carried out after preparing described active component coating precursor immediately, Can also carry out (i.e. before desulfurization is adsorbed) before use.Owing to transition metal promoter easily aoxidizes, And the transition metal promoter in active component coating precursor exists in the form of an oxide, therefore for ease of fortune Defeated, preferably the reduction of active component coating precursor is carried out before carrying out desulfurization absorption.Described reduction treatment is Make the metal in the oxide of transition metal promoter substantially exist with reduction-state, obtain the de-of the present invention Sulfur catalyst.Under preferable case, the condition that active component coating precursor reduces in a hydrogen atmosphere is included: Hydrogen content is the reducing gas of 10-60 volume %, and the temperature of reduction is 250-550 DEG C, the pressure of reduction For 0.2-5MPa, the time of reduction is 0.5-6 hour；The temperature preferably reduced is 300-450 DEG C, also Former pressure is 0.5-3.5MPa, and the time of reduction is 1-3 hour.

According to the present invention, described transition metal promoter can make the organic sulfur conversion in sulfur-bearing hydrocarbon be sulfuration Hydrogen.Preferably, described transition metal promoter can be at least one in cobalt, nickel, ferrum and manganese.More Preferably, described transition metal promoter is nickel.

According to the present invention, described substrate contain the BEA structure of 70-90 weight % and FAU structure point At least one in son sieve and the silica binder of 10-30 weight %, under preferable case, BEA structure With the molecular sieve of FAU structure selected from X molecular sieve or/and Y type molecular sieve.

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.

Although it should be noted that above-mentioned silica source may contain aluminium oxide, but the present invention aoxidizes The content of aluminum does not include the amount of aluminium oxide contained in above-mentioned silica source, and the content of aluminium oxide only includes The amount of the aluminium oxide formed by alumina source.The amount of aluminium oxide contained in silica source still can be regarded as oxygen The amount in SiClx source.Method the most provided by the present invention prepare desulphurization catalyst in each component content according to Inventory calculates.

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.

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 transition metal promoter.Ordered structure catalyst may be used for sulfur-bearing hydrocarbon As fixing beds in desulfurization reactor, the sulfur-bearing hydrocarbon of flowing and hydrogen donor can flow and pass through Ordered structure catalyst bed, i.e. can flow by the duct in ordered structure carrier, and in cell walls The active component coating of distribution 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 use fixed bed reactors During as reactor, the catalyst system of the present invention is seated in fixed bed reactors, wherein, described in urge Ordered structure catalyst in agent system is presented in beds, in described catalyst system Desulfurizing assistant agent with fluidisation form pass through beds.

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, contained The ordered structure catalyst crossing metallic promoter agent only need to operate under sulfur-bearing hydrocarbon desulfurization reaction condition, and desulfurization Auxiliary agent needs alternate repetition under the conditions of sulfur-bearing hydrocarbon desulfurization reaction condition and regenerative response to operate.So Can avoid when transition metal promoter and desulfurizing assistant agent are prepared as one, transition metal promoter must not The most repeatedly experience the situation of oxidation regeneration-reduction, and repeatedly experience oxidation regeneration-reduction and can make transition metal Accelerator is assembled, and reduces 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 also includes: under the conditions of regenerative response, in a regenerator taking off described load sulfur Sulfur auxiliary agent and rejuvenating gas contacts, obtain the desulfurizing assistant agent of regeneration.

According to the present invention, the condition for desulfurizing assistant agent regeneration can be the carded sliver more commonly used in the art Part.Under preferable case, described regenerative response condition includes: regeneration temperature is 300-800 DEG C, regeneration pressure Power is 0.1-3MPa, and regeneration gas feed volume air speed is 500-1500h^-1, regeneration gas is oxygenous Body.Preferably regeneration temperature is 350-600 DEG C, and regeneration pressure is 0.1-1MPa, regeneration gas feed volume Air speed is 500-1000h^-1.Regeneration gas can be that at least one is selected from oxygen, air, oxygen and inertia The gas of the mixture of the mixture of gas, air and noble gas.Above-mentioned condition can preferably remove Carry 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 , also it is in order at 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, the method for the present invention is additionally included in desulfurizing assistant agent and the regeneration gas of described load sulfur After contact, the desulfurizing assistant agent of described regeneration is carried out atmosphere displacement and pressurization, make the desulfurization of described regeneration help It is high pressure hydrogen atmosphere that agent enters from low-pressure oxygen atmosphere, and returns in described sulfur-bearing hydrocarbon desulfurization reactor.

In the case of according to the invention it is preferred to, the method for the present invention be additionally included in by sulfur-bearing hydrocarbon and hydrogen donor with Before catalyst system contact, under the reducing conditions, by the ordered structure catalyst in described catalyst system Contact with reducing gas.The transition metal promoter in ordered structure catalyst can be made with reduction-state form Exist, beneficially 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 More than 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 by through entering, from displacement gas, noble gas (the noble gas for example, nitrogen that pipe is passed through Gas) displacement after from hydrogen gas environment enter low pressure inert atmosphere become desulfurizing assistant agent to be generated, displace Gas is sent to combustion furnace through displacement gas discharge pipe 19 and burns, and desulfurizing assistant agent to be generated is delivered to regenerator feed Tank 22, then enter regenerator 25 by spent agent feed pipe 23, oxygen-containing gas is entered by regeneration gas simultaneously Trachea 24 enters regenerator 25 from the bottom of regenerator 25, and desulfurizing assistant agent to be generated and oxygen-containing gas are in regeneration In device 25 and flow contact through burning sulfur, burning and discharge sulfur-containing smoke gas and regenerative sulfur binding auxiliary agent, sulfur-containing smoke gas after carbon After regenerator 25 top separates with regenerative sulfur binding auxiliary agent through smoke discharge pipe 26 be delivered to sulfur system processed or Alkali cleaning removing Sox, regenerative sulfur binding auxiliary agent is defeated through regenerative agent discharge pipe 27 from regenerator 25 top emulsion zone Deliver in Regenerator receiver 28, after promoting with noble gas, be delivered to locking hopper 18, at locking material In bucket 18, regenerative sulfur binding auxiliary agent enters after being replaced by the hydrogen stripped being passed through from displacement gas entrance pipe and boost Hydrogen gas 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 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 separation_x.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 the Y type molecular sieve powder of 1.01kg (Beijing Chemical Plant produces, Containing butt 1.0kg) and 1kg deionized water mix homogeneously, wet ball grinding becomes serosity, and compound particles is straight Footpath d90=8 micron；

Molecular sieve pulp will add 210 grams of waterglass (silicon oxide-containing 15 weight %, middle Effect of Catalysis In Petrochemistries Agent asphalt in Shenli Refinery produces, and modulus is 3.2, and particle diameter is 1～5nm, and mean diameter is 3nm), In terms of silicon oxide, the addition of waterglass is 25 weight % of Y type molecular sieve weight, stirs 10 minutes, Add polyglycol solution 3.24 grams (in solution, the percetage by weight of Polyethylene Glycol is 2 weight %), should The addition of solution is 3 weight % of molecular sieve, stirs and within 20 minutes, obtains catalyst coat and prepare Mix slurry (coating slurry).

(cordierite honeycomb carries to prepare mix slurry coating honeycomb substrate with obtained catalyst coat Body, 31 holes/square centimeter, non-metal chemical mechinery works of Jiangsu honeycomb pottery subsidiary factory product) all Inner surfaces of pores, blows off honeycomb substrate outer surface by compressed air (pressure is 0.4MPa, lower same), Dry 2 hours at 120 DEG C, roasting 1 hour at 650 DEG C, obtain the ordered structure carrier with substrate, Coating accounts for the 5wt% of whole cellular supported catalyst.SiO in this coating₂Content is 20wt%, Y type Molecular sieve content is 80wt%；

Ni (the NO that 364 grams have been configured₃)₂Aqueous solution, stain is dipped into the ordered structure carrier having been coated with substrate All inner surfaces of pores, blow off honeycomb substrate outer surface by compressed air, dry 2 hours at 120 DEG C, Roasting 1 hour at 650 DEG C, obtains the ordered structure catalyst of active constituent element.

This ordered structure catalyst, on active component coating, nickel content is 80 weight %, Y type molecular sieve Content is 16 weight %, SiO₂Content is 4 weight %.In catalyst, active component coating content is 25 Weight %.

Desulfurizing assistant agent uses following methods to prepare:

By 6.38 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, containing butt 6.3 kilograms) and 8.5 thousand The mixing of gram deionized water, obtains zinc oxide serosity after stirring 30 minutes.

Take aluminium oxide 1.60 kilograms (Shandong Aluminum Plant produces, containing butt 1.20 kilograms) and the height of 3.0 kilograms Ridge soil (containing butt 2.50 kilograms) (deriving from Qilu Petrochemical catalyst plant) under agitation mixes, then adds After entering 3.6 kilograms of mix homogeneously of deionized water, add 300 milliliter of 30 weight % hydrochloric acid (chemical pure, Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours, add zinc oxide After serosity mixing, stirring obtains auxiliary agent serosity in 1 hour.

Above-mentioned auxiliary agent serosity uses Niro Bowen Nozzle Tower^TMThe 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 63.0 weight %, aluminium 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

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

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 the X-type molecular sieve powder of 3.29kg, (middle Effect of Catalysis In Petrochemistry agent is neat Shandong branch company produces, containing butt 2.8kg) and 3kg deionized water mix homogeneously, wet ball grinding becomes serosity, Compound particles diameter d90=8 micron；

Molecular sieve pulp will add 1.76kg waterglass (silicon oxide-containing 15 weight %, middle Effect of Catalysis In Petrochemistry Agent asphalt in Shenli Refinery produces, and modulus is 3.2, and particle diameter is 1～5nm, and mean diameter is 3nm), with The addition of silicon oxide meter waterglass is 42.8 weight % of X-type molecular sieve weight, stirs 10 minutes, Add polyglycol solution 9.07 grams (in solution, the percetage by weight of Polyethylene Glycol is 2 weight %), should The addition of solution is 3 weight % of molecular sieve, stirs and within 20 minutes, obtains catalyst coat and prepare Mix slurry (coating slurry).

(cordierite honeycomb carries to prepare mix slurry coating honeycomb substrate with obtained catalyst coat Body, 31 holes/square centimeter, non-metal chemical mechinery works of Jiangsu honeycomb pottery subsidiary factory product) all Inner surfaces of pores, blows off honeycomb substrate outer surface by compressed air (pressure is 0.4MPa, lower same), Dry 2 hours at 120 DEG C, roasting 1 hour at 650 DEG C, obtain the ordered structure carrier with substrate, Coating accounts for the 19.6wt% of whole cellular supported catalyst.SiO in this coating₂Content is 30wt%, X Type molecular sieve content is 70wt%；

Ni (the NO that 152 grams have been configured₃)₂Aqueous solution, stain is dipped into the ordered structure carrier having been coated with substrate All inner surfaces of pores, blow off honeycomb substrate outer surface by compressed air, dry 2 hours at 120 DEG C, Roasting 1 hour at 650 DEG C, obtains the ordered structure catalyst of active constituent element.

This ordered structure catalyst, on active component coating, nickel content is 30 weight %, X-type molecular sieve Content is 49 weight %, SiO₂Content is 21 weight %.In catalyst, active component coating content is 28 Weight %.

Desulfurizing assistant agent uses following methods to prepare:

By 3.04 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, containing butt 3.0 kilograms) and 4.5 thousand The mixing of gram deionized water, obtains zinc oxide serosity after stirring 30 minutes.

Take aluminium oxide 4.53 kilograms (Shandong Aluminum Plant produces, containing butt 3.4 kilograms) and the height of 4.2 kilograms Ridge soil (containing butt 3.50 kilograms) (deriving from Qilu Petrochemical catalyst plant) under agitation mixes, then adds After entering 8.0 kilograms of mix homogeneously of deionized water, add 850 milliliter of 30 weight % hydrochloric acid (chemical pure, Beijing Chemical Plant produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours, add zinc oxide After serosity mixing, stirring obtains auxiliary agent serosity in 1 hour.

Above-mentioned auxiliary agent serosity uses Niro Bowen Nozzle Tower^TMThe 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 %, aluminium oxide 35.0 weight %, Kaolin 35.0 weight %.

Reaction condition is with embodiment 1, and reaction result is shown in Table 2.

Embodiment 5

(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 the Beta molecular sieve powder of 1.69kg, (middle Effect of Catalysis In Petrochemistry agent is long Ridge branch company produces, containing butt 1.47kg) and 1.5kg deionized water mix homogeneously, wet ball grinding pulping Liquid, compound particles diameter d90=8 micron；

Molecular sieve pulp will add 239 grams of waterglass (silicon oxide-containing 15 weight %, middle Effect of Catalysis In Petrochemistries Agent asphalt in Shenli Refinery produces, and modulus is 3.2, and particle diameter is 1～5nm, and mean diameter is 3nm), with The addition of silicon oxide meter waterglass is 11.11 weight % of Beta molecular sieve, stirs 10 minutes, Add polyglycol solution 4.86 grams (in solution, the percetage by weight of Polyethylene Glycol is 2 weight %), should The addition of solution is 3 weight % of molecular sieve, stirs and within 20 minutes, obtains catalyst coat and prepare Mix slurry (coating slurry).

(cordierite honeycomb carries to prepare mix slurry coating honeycomb substrate with obtained catalyst coat Body, 31 holes/square centimeter, non-metal chemical mechinery works of Jiangsu honeycomb pottery subsidiary factory product) all Inner surfaces of pores, blows off honeycomb substrate outer surface by compressed air (pressure is 0.4MPa, lower same), Dry 2 hours at 120 DEG C, roasting 1 hour at 650 DEG C, obtain the ordered structure carrier with substrate, Coating accounts for the 8wt% of whole cellular supported catalyst.SiO in this coating₂Content is 10wt%, Beta Molecular sieve content is 90wt%；

Ni (the NO that 217 grams have been configured₃)₂Aqueous solution, stain is dipped into the ordered structure carrier having been coated with substrate All inner surfaces of pores, blow off honeycomb substrate outer surface by compressed air, dry 2 hours at 120 DEG C, Roasting 1 hour at 650 DEG C, obtains the ordered structure catalyst of active constituent element.

This ordered structure catalyst, on active component coating, nickel content is 60 weight %, Beta molecular sieve Content is 36 weight %, SiO₂Content is 4 weight %.In catalyst, 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) and 10 kilograms Deionized water mixes, and obtains zinc oxide serosity after stirring 30 minutes.

Take aluminium oxide 0.667 kilogram (Shandong Aluminum Plant produces, containing butt 0.5 kilogram) and the height of 1.2 kilograms Ridge soil (containing butt 1.0 kilograms) (deriving from Qilu Petrochemical catalyst plant) under agitation mixes, is subsequently adding After 1.0 kilograms of mix homogeneously of deionized water, add hydrochloric acid (chemical pure, the north of 100 milliliter of 30 weight % Chemical plant, capital produce) stirring acidifying 1 hour after be warming up to 80 DEG C aging 2 hours, add zinc oxide paste After liquid mixing, stirring obtains auxiliary agent serosity in 1 hour.

Above-mentioned auxiliary agent serosity uses Niro Bowen Nozzle Tower^TMThe 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 78.0 weight %, aluminium oxide 8.0 weight %, Kaolin 14.0 weight %.The same embodiment of reaction condition 1, 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 %) use Fluidized-bed reactor carries out gasoline desulphurization reaction.

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 5.8ppm, and loss of octane number averagely only has 0.09 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 6.5ppm, and loss of octane number averagely only has 0.1 unit.Although reaction pressure and anti- Being significantly increased of hydrogen-oil ratio is answered to be likely to result in anti-knock index loss increasing, but anti-owing to improve simultaneously Answering temperature, it is suppressed that the carrying out of hydrogenation reaction, the cracking ability of catalyst strengthens simultaneously, small molecule hydrocarbon class Increasing, therefore the loss of octane number of product the most only reduces 0.1 unit, and bulk product liquid is received and still protected Hold 99.8%.

In embodiment 3, owing on ordered structure catalyst, the reducing degree of promoter metals increases, transition Metal promoted agent content increases, and makes the most also to have higher desulphurizing activated.During because attaching most importance to Air speed increases, and 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, Catalyst deactivation rate slows down.Product sulfur content is only 3.9ppm at the end of reaction, and antiknock refers to Number loss only 0.09 unit.Bulk product liquid is received and is maintained at 99.8%.

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 6.5ppm 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.

The catalyst system that the present invention provides can have the most desulphurizing activated and desulfurization stability.

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

1. a catalyst system for sulfur-bearing hydrocarbon desulfurization, this catalyst system includes: desulfurizing assistant agent and rule Whole 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 work Property component coating contains transition metal promoter and the substrate of 10-70 weight % of 30-90 weight %, institute State the metal that transition metal promoter is VIIB race and/or VIII；Described substrate contains 70-90 weight At least one in the BEA structure of % and the molecular sieve of FAU structure and the silicon oxide of 10-30 weight % Binding agent；On the basis of the gross weight of described desulfurizing assistant agent, described desulfurizing assistant agent contains 5-40 weight % In aluminium oxide, the silica source of 5-40 weight % and IIB, VB of 30-90 weight % and group vib extremely The oxide of few a kind of metal, described desulfurizing assistant agent is the microsphere of mean diameter 20-200 micron；Described Desulfurizing assistant agent is 1-9:1 with the weight ratio of the active component coating of described ordered structure catalyst.

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 transition metal promoter is At least one in cobalt, nickel, ferrum and manganese.

Catalyst system the most according to claim 1, wherein, described BEA structure or FAU The molecular sieve of structure is X molecular sieve and/or Y type molecular sieve.

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 8, wherein, described silica source be kieselguhr, In expanded perlite, Kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel at least one Kind.

Catalyst system the most 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 11. 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 1-10 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.

12. methods according to claim 11, 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.

13. methods according to claim 11, 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.

14. methods according to claim 13, 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.

15. according to the method described in claim 13 or 14, and wherein, the method also includes: described Before carrying desulfurizing assistant agent and the rejuvenating gas contacts of 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 enter low pressure inert atmosphere from high pressure hydrogen atmosphere.

16. according to the method described in claim 13 or 14, and wherein, the method also includes: described After carrying desulfurizing assistant agent and the rejuvenating gas contacts of sulfur, the desulfurizing assistant agent of described regeneration is carried out atmosphere displacement and Pressurization, makes the desulfurizing assistant agent of described regeneration enter high pressure hydrogen atmosphere from low-pressure oxygen atmosphere, and returns institute State in sulfur-bearing hydrocarbon desulfurization reactor.

17. methods according to claim 11, 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.

18. methods according to claim 17, 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.

19. methods according to claim 11, 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 separating_x, 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.

20. methods according to claim 19, wherein, described sulfur-bearing hydrocarbon desulfurization reactor is rule Whole structural response device, described regenerator is fluid bed regenerator.