CN101766985A - Desulfurizing sorbent and preparation method and application thereof - Google Patents
Desulfurizing sorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a sorbent for desulfurizing cracked spirit and diesel engine fuel. The sorbent has good abrasion resistance and desulfurizing activity. With reference of the gross weight of sorbent, the desulfurizing sorbent includes the following components: 5-35wt percent of alumina; 3-30wt percent of monox; 10-80wt percent of metal oxide, at least one type selected from the families of IIB, VB and VIB; 3-30wt percent of accelerant metal, at least one type selected from the families of VIIB and VIII; and 0.5-10wt percent of metal oxide from the IIA family.
Description
Technical field
The present invention relates to a kind of adsorbent composition that is applicable to desulfurization in cracking gasoline and diesel fuel and preparation method thereof.
Background technology
The oxysulfide that produces behind the combustion of sulfur in the vehicle fuel, active also can the making it that can suppress the noble metal catalyst in the vehicle exhaust converter takes place irreversibly to poison.Thereby make and contain unburned non-methane hydrocarbon and nitrogen oxide and carbon monoxide in the vehicle exhaust, these discharging gas are then formed photochemical fog easily by the day photocatalysis, cause acid rain, the oxysulfide itself in the atmosphere also is the one of the main reasons that forms acid rain simultaneously.Along with the pay attention to day by day of people to environmental protection, environmental regulation is also day by day strict, and the sulfur content of reduction gasoline and diesel oil is considered to one of most important measure that improves air quality.
Most sulphur comes from hot-working petroleum in China's gasoline, is mainly catalytically cracked gasoline, so the minimizing of sulfur content helps to reduce the sulfur content of these gasoline in the cracking gasoline.The existing gasoline products standard of China is GB 17930-2006 " motor petrol ", and this standard is further made restriction to sulfur in gasoline content, requires on December 31st, 2009, and sulfur in gasoline content drops to 50ppm.In this case, catalytically cracked gasoline must just can meet environmental protection requirement through deep desulfuration.
In order to guarantee the combustibility of motor vehicle fuel, in the sulfur content that reduces motor vehicle fuel, its octane number (comprising ROM and MON) is reduced thereby also should avoid its olefin(e) centent to change as far as possible.To the negative effect of olefin(e) centent generally is owing to remove thiophenes (comprising thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and alkyl diphenyl bithiophene) and cause hydrogenation reaction simultaneously and cause.In addition, the aromatic hydrocarbons that also needs to avoid described condition to make cracking gasoline loses by saturated, and therefore optimal method is to keep its octane number when realizing desulfurization.
On the other hand, the hydrogenation of hydrodesulfurization and unsaturated hydrocarbons all needs to consume hydrogen, and this makes the running cost of desulfurization increase.Therefore the method that needs a kind of desulfurization under the lower situation of hydrogen-consuming volume provides more economical method thereby handle for cracking gasoline and diesel fuel, such as S Zorb adsorption desulfurize technology.
The method of fixed bed is often adopted in desulfurization from liquid state traditionally, but the reaction uniformity of this method and regeneration all have tangible inferior position.Compare the advantage that fluidized-bed process has aspects such as better heat transfer and pressure drop with fixed-bed process, therefore have broad application prospects.Fluidized-bed reactor is general to adopt granular reactant, but for the great majority reaction, used reactant does not generally have enough wearabilities.Therefore, find anti-wear performance well to have the adsorbent of better desulfurization performance significant simultaneously.
Patent CN 1048418, and CN 1151333 provides a kind of novel absorbing composition that contains zinc oxide, silica, colloidal oxide and promoter, and this preparation of adsorbent method is provided.But this method adopts the way of pressure forming to prepare the particle of fluidisation, and pore creating material inflammable during simultaneously by adding heating in colloid is to improve its pore volume.The particle that this method is prepared is bigger, is the 100-300 micron, and this is not best for fluid mapper process.And this method improves pore volume by adding inflammable pore creating material, makes particle broken easily, and intensity is relatively poor.
Patent US 6150300, and CN 1130253, and the adsorbent of introducing among the CN 1258396 is: the granular adsorption agent composition that comprises the mixture of zinc oxide, silica, aluminium oxide, reduction valence state nickel or cobalt; Its preparation method mainly is to adopt method such as shearings that silica, aluminium oxide and zinc oxide are mixed and prepare solid particle by comminutor, makes adsorbent thereby flood nickel behind the drying and roasting.Though the adsorbent of these patent introductions has desulfurization performance preferably,, mainly be that tear strength is not introduced in patent for its physical and chemical performance.
Adopt promoter metals such as cobalt and nickel dipping to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide among the patent CN 1208124, reduction accelerator under suitable temperature prepares the adsorbent that is used for removing cracking gasoline sulfide then.Improve the abrasion resistance properties of adsorbent by zinc oxide content and binding agent (being mainly aluminium oxide) in the adjusting adsorbent.Among the patent CN 1627988 these several compounds that mainly generate have been carried out detailed discussion under reaction condition, and the particle that this patent adopts spray-dired method to prepare more is applicable to fluid bed aspect physico-chemical property.In patent CN 1856359, CN 1871063, describe the adsorbent and its preparation method of similar composition in detail.
In these preparation of adsorbent methods, by adding aluminium oxide, improve the intensity of adsorbent with zinc oxide adhesion moulding, add expanded perlite simultaneously and guarantee physico-chemical property.But because there is chemical reaction in zinc oxide in the adsorption desulfurize process, cause structure fragmentation in the course of reaction, make the active on the low side of adsorbent.Therefore, preparing the adsorbent that has high desulphurizing activated and high abrasion strength resistance simultaneously is the target that those skilled in the art make great efforts.
Summary of the invention
The invention provides a kind of adsorbent that is used for removing from cracking gasoline and diesel fuel sulphur, this adsorbent has high abrasion strength resistance and desulphurizing activated.
The present invention also provides above-mentioned preparation of adsorbent method.
The present invention also provides the application of above-mentioned adsorbent.
Desulfuration adsorbent provided by the invention is a benchmark with the adsorbent gross weight, comprises following composition:
1) aluminium oxide, content are 5-35wt%;
2) silica, content are 3-30wt%;
3) at least a metal oxide that is selected from II B, VB and group vib, content is 10-80wt%;
4) at least a promoter metals that is selected from VIIB and VIII family, content is 3-30wt%;
5) at least a IIA family metal oxide, content is 0.5-10wt%.
Under the preferable case, the content of aluminium oxide is 10-25wt%, and the content of silica is 10-20wt%, and the content of metal oxide is 35-65wt%, and the content of metallic promoter agent is 8-20wt%, and IIA family metal oxide content is 1-5wt%.
The metal oxide of the described II of being selected from B, VB and group vib is the metal oxide with storage sulphur performance, the oxide of elements such as preferred at least a vanadium, zinc or molybdenum, most preferably zinc oxide.
Described promoter metals can be any metal that oxidation state sulphur can be reduced to hydrogen sulfide, can be selected from the metal of VIIB and VIII family, preferably comprises at least a metal that is selected from cobalt, nickel, iron and the manganese, most preferably contains nickel in the promoter metals.
The oxide of described IIA family's alkaline earth oxide preferably magnesium and/or calcium.
Preparation of adsorbent method provided by the invention comprises:
(1) water, acid are mixed with binding agent, or also with clay, silica source and IIA family metallic compound at least a the mixing, the formation slurries wear out, and obtain the acidifying slurries;
(2) clay, silica source and the IIA family metallic compound of adding do not mix the formation carrier mixture with the metal oxide that is selected from II B, VB and group vib and in step (1) with above-mentioned acidifying slurries;
(3) make the said mixture moulding, and drying and roasting, carrier formed;
(4) introducing contains the compound that is selected from VIIB and VIII family promoter metals on above-mentioned carrier, and drying and roasting, obtains the adsorbent precursor;
(5) above-mentioned adsorbent precursor is reduced under hydrogeneous atmosphere, promoter metals is existed to go back ortho states basically.
Described silica source is the natural minerals of silica content greater than 70wt%, can also contain other component such as Al in the natural minerals
2O
3, K
2O, CaO, MgO, Fe
2O
3, TiO
2Deng.Described silica source can be selected from one or more in diatomite, Ludox, silicon gel, macropore silicon oxide and the expanded perlite etc., preferred diatomite and/or expanded perlite.
Described IIA family metallic compound can be nitrate, chloride, formates, acetate of IIA family metal etc.Described IIA family's metal preferably magnesium and/or calcium.
Described clay can be selected from one or more in kaolin, rectorite, Yun Mengshi, bentonite, the imvite etc., preferred kaolin.Alumina content can also contain other component such as SiO greater than 40wt% in these clays
2, K
2O, CaO, MgO, Fe
2O
3, TiO
2Deng.
Described binding agent is meant the material that can form heat-resistant inorganic oxide after the roasting, and wherein heat-resistant inorganic oxide is one or more in aluminium oxide, silica and the amorphous silicon aluminium, preferred aluminium oxide.In the preferred hydrated alumina of described binding agent, aluminium colloidal sol, boehmite (boehmite), false boehmite (boehmite), hibbsite, the amorphous hydroted alumina one or more, after these multi-form binding agent roastings with γ-Al
2O
3Form exist.These binding agents are conventionally known to one of skill in the art.
The described oxide that is selected from the elements such as the preferred at least a vanadium of metal oxide, zinc or molybdenum of II B, VB and group vib can be an oxide powder, also can be the oxide slurries that prepare in advance, and these methods are conventionally known to one of skill in the art.
Described promoter metals can be any metal that oxidation state sulphur can be reduced to hydrogen sulfide, can be selected from the metal of VIIB and VIII family, preferably comprises one or more metals that are selected from cobalt, nickel, iron and the manganese at least, most preferably contains nickel in the promoter metals.
The compound of described promoter metals is the material that can be converted into metal oxide under roasting condition, can be selected from acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of promoter metals, and two or more mixture etc. wherein.
According to preparation method provided by the invention, clay, silica source, binding agent, IIA family metallic compound, be selected from the metal oxide of II B, VB and group vib and be selected from VIIB and the consumption of the compound of VIII family promoter metals makes in the adsorbent finally make, with the adsorbent gross weight is benchmark, comprises following composition:
1) aluminium oxide, content are 5-35wt%;
2) silica, content are 3-30wt%;
3) at least a metal oxide that is selected from II B, VB and group vib, content is 10-80wt%;
4) at least a promoter metals that is selected from VIIB and VIII family, content is 3-30wt%;
5) at least a IIA family metal oxide, content is 0.5-10wt%.
Under the preferable case, the content of aluminium oxide is 10-25wt%, and the content of silica is 10-20wt%, and the content of metal oxide is 35-65wt%, and the content of metallic promoter agent is 8-20wt%, and IIA family metal oxide content is 1-5wt%.
It is characterized in that clay is 0.2-1.2 with the ratio of the weight of binding agent: 1, preferred 0.4-0.8: 1.Silica source is 0.5-1.5 with the ratio of the weight of binding agent: 1; Preferred 0.8-1.0: 1.
Specifically, adsorbent of the present invention can prepare in accordance with the following methods
In step (1) and (2), described acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, is preferably in hydrochloric acid, nitric acid, phosphoric acid and the acetic acid one or more.Described acid preferably adds after other component, adds fashionable needs and fully stirs.The consumption of acid makes the pH value of slurries for 1-5, is preferably 1.5-4.Aging temperature is generally 60-80 ℃, the general 1-3 of ageing time hour.It is 10-20wt% that the consumption of water makes the concentration of slurries.
The method of described formation carrier mixture can adopt various orders, and its medium clay soil, silica source and IIA family metallic compound can add in step 1, also can add in step 2.Wherein a kind of preferable methods comprises: a, by step (1) water, acid, binding agent and clay, silica source are mixed, and aging, form the acidifying slurries; B adds metal oxide and the IIA family metallic compound that is selected from IIB, VB and group vib in above-mentioned slurries, form carrier mixture.Another kind of preferable methods comprises: a, and by step (1) clay, binding agent and acid solution are mixed, aging, form the acidifying slurries; B mixes silica source and IIA family metallic compound, and 400-600 ℃ of oven dry roasting down, obtains pretreated silica source; C adds at least a II B, VB and group vib metal oxide and the pretreated silica source of being selected from the acidifying slurries, form carrier mixture.
In the step (3), make the gained carrier mixture be shaped to extrudate, sheet, pill, ball or micro-spherical particle.For example, when described carrier mixture is dough or paste mixture, can make described mixture moulding (preferred extrusion molding) form particle, preferred diameter is at 1.0-8.0mm, length makes the extrudate of gained carry out drying, roasting at the cylindrical extrudate of 2.0-5.0mm then.If the gained mixture is the wet mixture form, can make this mixture multiviscosisty, through the super-dry aftershaping.More preferably carrier mixture is the slurries form, and forming granularity by spray-drying is the microballoon of 20-200 micron, reaches the purpose of moulding.For the ease of spray-drying, the solid content of dry preceding slurries is 10-50wt%, is preferably 20-50wt%.
The drying means of the carrier mixture of moulding and condition are conventionally known to one of skill in the art, for example Gan Zao method can be dry, oven dry, forced air drying.Dry temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.
The roasting condition of the carrier mixture of moulding also is conventionally known to one of skill in the art, and in general, sintering temperature is 500-800 ℃, is preferably 650-750 ℃, and roasting time was at least 2 hours, was preferably 2-100 hour, more preferably 2-10 hour.
In the step (4), can adopt the method that well known to a person skilled in the art dipping or precipitation on carrier, to introduce promoter metals.Described dipping method is solution or the carrier of suspension impregnation after roasting with the compound that contains promoter metals.Described intermediate processing is that solution or the suspension that will contain the compound of promoter metals mix with adsorbing agent carrier, adds ammoniacal liquor then metallic compound is deposited on the carrier.
In the step (4), the carrier of introducing the promoter metals compound carries out drying under about 50-300 ℃, and preferred baking temperature is 100-250 ℃, is about 0.5-8 hour drying time, more preferably from about 1-5 hour.After the drying, under the condition that has oxygen or oxygen-containing gas to exist about 300-800 ℃, more preferably carry out roasting under 450-750 ℃ the temperature, general about 0.5-4 hour of needed time of roasting, preferred 1-3 hour, be removed and promoter metals is converted into metal oxide until volatile materials, obtain the adsorbent precursor.
In the step (5), the adsorbent precursor is reduced under 300-600 ℃ of hydrogeneous atmosphere, promoter metals is existed to go back ortho states basically, obtain adsorbent of the present invention.Preferred reduction temperature is 400-500 ℃, and hydrogen content is 10-60vol.%, recovery time 0.5-6 hour, and more preferably 1-3 hour.
The present invention also provides the sulfur method of a kind of cracking gasoline or diesel fuel, be included under 350-500 ℃, under preferred 400-450 ℃ the sulfur-bearing raw material is fully contacted with adsorbent of the present invention, the sulphur in this process in the raw material is adsorbed on the adsorbent, thereby obtains the product of low sulfur content.Wherein can reuse after this regenerative process of adsorbent process OR.
Said contact is preferably carried out in fluid bed.
It is 40 to 210 ℃ hydrocarbon or its any cut that term used herein " cracking gasoline " means boiling range, is from making bigger hydrocarbon molecule be cracked into the product of the heat or the catalytic process of less molecule.The thermal cracking process that is suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of the catalytic cracking process that is suitable for includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, the catalytically cracked gasoline of Shi Yonging includes but not limited to coker gasoline, pressure gasoline, visbreaking gasoline, fluid catalystic cracking gasoline and residual oil cracking gasoline and combination thereof.Can be during in some cases, in the methods of the invention as hydrocarbon-containifluids fluids with described cracking gasoline fractionation and/or hydrotreatment before desulfurization.
It is 170 to 450 ℃ the hydrocarbon mixture or the liquid of its any fractional composition that term used herein " diesel fuel " means boiling range.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil and hydrotreatment diesel oil etc. and combination thereof.
The normal organosulfur compound that exists in term used herein " sulphur " any type of element sulphur of representative such as hydrocarbon-containifluids fluids such as cracking gasoline or the diesel fuel.The sulphur that exists in the hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS
2), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and alkyl diphenyl bithiophene, and the normal bigger thiophenes of molecular weight that exists in the diesel fuel.
Adsorbent provided by the invention has high abrasion strength resistance and desulphurizing activated, can increase the service life greatly, is applicable to the adsorption desulfurize process.
The specific embodiment
Following example will the present invention is described further, but therefore do not limit the present invention.Among the embodiment, by the composition of XRF methods analyst adsorbent.
Embodiment 1
Get 0.80 kilogram of expanded perlite (world mining company, M27 contain 0.79 kilogram of butt, silica content 72wt%, alumina content 19wt%, all the other are K
2O, MgO, Fe
2O
3Deng) and 450 gram magnesium nitrate hexahydrates mix in 1.5 kg water solution and the solution evaporate to dryness, take out the expanded perlite of mixture after 500 ℃ of following roastings obtained handling in 1 hour then.
0.71 kilogram kaolin (Suzhou kaolin factory, S1 contain 0.59 kilogram of butt, alumina content 44wt.%, and silica content 50wt.%, all the other are CaO, Fe
2O
3, TiO
2Deng), after hydrated alumina 1.15 kilograms (the SB powder contains 0.78 kilogram of butt) and 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 75 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, add the expanded perlite after 3.5 kilograms of zinc oxide (containing 3.43 kilograms of pure zinc oxides) powder and the above-mentioned processing, mix the back and stir after 1 hour and obtaining the carrier mixture slurries.
Described carrier mixture slurries adopt Niro Bowen Nozzle Tower
TMThe spray dryer of model carries out spray-drying, is spray-drying pressure 8.0 to 5.5MPa, and inlet temperature is below 480 ℃, and outlet temperature is about 150 ℃.The microballoon that is obtained by spray-drying obtained adsorbing agent carrier in 1 hour 735 ℃ of following roastings.
3.24 kilograms adsorbing agent carriers (3.0 kilograms of butts) are flooded with 3.04 kilograms of Nickelous nitrate hexahydrates, 1.2 kilograms of deionized water solutions, the mixture that obtains after 4 hours, 1 hour can make adsorbent precursor in 735 ℃ of roastings of air atmosphere through 180 ℃ of dryings.Adsorbent precursor reductase 12 in 425 ℃ hydrogen atmosphere hour can obtain adsorbent, and this adsorbent is designated as adsorbent A 1.
Composition by XRF methods analyst adsorbent.The chemical composition of adsorbent A 1 is that zinc oxide content is 51.2wt%, and alumina content is 17.8wt%, and silica content is 12.9wt%, and nickel (calculating with metallic nickel) is 15.5wt%, and magnesia is 1.0wt%.
Embodiment 2
Get 0.92 kilogram of expanded perlite (world mining company, M27, contain 0.91 kilogram of butt), 0.49 kilogram kaolin (Suzhou kaolin factory, S1 contain 0.41 kilogram of butt), 1.55 kilograms of (SB powder of hydrated alumina, contain 1.05 kilograms of butts) and after 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 90 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, add 3.16 kilograms of zinc oxide (containing 3.1 kilograms of pure zinc oxides) powder and 0.9 kilogram of magnesium nitrate hexahydrate, mix the back stirring and obtain the carrier mixture slurries after 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 2.Adsorbent A 2 chemical compositions are that zinc oxide content is 46.3wt%, and aluminium oxide 20.9wt%, silica content are 12.9wt%, and nickel (calculating with metallic nickel) is 16.2wt%, and magnesia is 2.1wt%.
Embodiment 3
Get 0.98 kilogram of diatomite (world mining company contains 0.88 kilogram of butt, silica content 86.7wt%, alumina content 7.5wt.%, all the other are CaO, Fe
2O
3Deng impurity) and 0.35 kilogram of calcium chloride (calculating) by the no crystallization water in 1.0 kg water solution, mix also the solution evaporate to dryness, take out the diatomite of mixture after 700 ℃ of following roastings obtained handling in 1 hour then.
0.66 kilogram kaolin (Suzhou kaolin factory, S1, contain 0.55 kilogram of butt), boehmite (contains 0.70 kilogram of butt for 1.12 kilograms, butt mainly consists of aluminium oxide) and after 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 70 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, add the diatomite after 3.59 kilograms of zinc oxide (containing 3.52 kilograms of pure zinc oxides) powder and the above-mentioned processing, mix the back and stir after 1 hour and obtaining the carrier mixture slurries.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 3.Adsorbent A 3 chemical compositions are that zinc oxide content is 51.8wt%, and aluminium oxide is 15.0wt%, and silica is 16.5wt%, and nickel (calculating with metallic nickel) is 12.9wt%, and calcium oxide is 2.6wt%.
Embodiment 4
Get 0.92 kilogram of expanded perlite (world mining company, M27 contain 0.91 kilogram of butt, silica content 72wt%, alumina content 19wt%, all the other are K
2O, MgO, Fe
2O
3Deng) and 900 gram magnesium nitrate hexahydrates mix in 2.5 kg water solution and the solution evaporate to dryness, take out the expanded perlite of mixture after 500 ℃ of following roastings obtained handling in 1 hour then.
0.49 kilogram kaolin (Suzhou kaolin factory, S1, contain 0.41 kilogram of butt), 1.55 kilograms of (SB powder of hydrated alumina, contain 1.05 kilograms of butts) and after 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 90 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, add the expanded perlite after 3.16 kilograms of zinc oxide (containing 3.1 kilograms of pure zinc oxides) powder and the above-mentioned processing, mix the back and stir after 1 hour and obtaining the carrier mixture slurries.
Introduce active component nickel with reference to the method for embodiment 2 then, this adsorbent is designated as A4.The composition of adsorbent A 4 is consistent with the composition of A2.
Comparative Examples 1
With embodiment 1 contrast, difference is not add magnesium nitrate.
0.71 kilogram kaolin (Suzhou kaolin factory, S1, contain 0.59 kilogram of butt), 1.15 kilograms of (SB powder of hydrated alumina, contain 0.78 kilogram of butt) and after 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 75 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, add 3.5 kilograms of zinc oxide (containing 3.43 kilograms of pure zinc oxides) powder and 0.8 kilogram of expanded perlite (containing 0.79 kilogram of butt), mix the back stirring and obtain the carrier mixture slurries after 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 1.It is 51.7wt% that adsorbent B 1 consists of zinc oxide content, and aluminium oxide is 18.0wt%, and silica is 13.0wt%, and nickel (calculating with metallic nickel) is 15.7wt%.
Comparative Examples 2
With embodiment 2 contrasts, difference is not add magnesium nitrate.
Get 0.92 kilogram of expanded perlite (world mining company, M27, contain 0.91 kilogram of butt), 0.49 kilogram kaolin (Suzhou kaolin factory, S1 contain 0.41 kilogram of butt), 1.55 kilograms of (SB powder of hydrated alumina, contain 1.05 kilograms of butts) and after 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 90 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, add 3.16 kilograms of zinc oxide (containing 3.1 kilograms of pure zinc oxides) powder, mix the back stirring and obtain the carrier mixture slurries after 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 2.Adsorbent B 2 chemical compositions are that zinc oxide content is 47.2wt%, and aluminium oxide is 21.4wt%, and silica is 13.2wt%, and nickel (calculating with metallic nickel) is 16.6wt%.
Comparative Examples 3
The preparation method of reference example 3, difference are not add calcium chloride.
0.66 kilogram kaolin (Suzhou kaolin factory, S1, contain 0.55 kilogram of butt), boehmite (contains 0.70 kilogram of butt for 1.12 kilograms, butt mainly consists of aluminium oxide) and after 9.0 kilograms of neutral waters (the pH value is 6-8) under agitation mix, add 70 gram red fuming nitric acid (RFNA)s (chemical pure, the Beijing Chemical Plant produces) and stirred and be warming up to more than 60 ℃ acidifying 1 hour.When treating that temperature is reduced to below 40 ℃, (world mining company contains 0.88 kilogram of butt, silica content 86.7wt% to add 3.59 kilograms of zinc oxide (containing 3.52 kilograms of pure zinc oxides) powder and 0.98 kilogram of diatomite, alumina content 7.5wt%, all the other are CaO, Fe
2O
3Deng impurity), mix the back stirring and obtain the carrier mixture slurries after 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 3.The zinc oxide content that consists of of adsorbent B 3 is 53.2wt%, and aluminium oxide is 15.4wt%, and silica is 16.9wt%, and nickel (calculating with metallic nickel) is 13.2wt%.
Embodiment 5
The adsorbent that adopts distinct methods to prepare is investigated abrasion strength resistance and two indexs of desulfurization performance.The intensity of adsorbent adopts straight tube wearing and tearing method to estimate, and its evaluation method is with reference to the method for RIPP 29-90 in " petrochemical industry analytical method (RIPP) experimental technique ", and numerical value is more little, shows that abrasion strength resistance is high more.In order better to represent the activity of adsorbent in the commercial Application process, adsorbent after the vulcanizing treatment is also carried out intensive analysis, concrete processing method is: the adsorbent that takes by weighing appropriate mass is positioned in the fluid bed, feed the gaseous mixture of hydrogen sulfide (50vol.%) and nitrogen (50vol.%), and be heated to 400 ℃ of vulcanizing treatment 1 hour.
Desulfurized effect is weighed with The product sulfur content, and sulfur content adopts the off-line chromatography in the product.
Adopt following method that the desulfurization performance of these adsorbents is estimated simultaneously.The adsorbent desulfurization performance adopts the little anti-experimental provision of fixed bed to estimate, and it is the catalytically cracked gasoline of 800ppm that the adsorption reaction raw material adopts sulphur concentration.The absorption test process adopts hydrogen atmosphere, and reaction temperature is 410 ℃, and the adsorption reaction weight space velocity is 4h
-1, in order accurately to characterize out the activity of adsorbent in industrial actual motion, processings of regenerating of back adsorbent finished in reaction, and the processing of regenerating is what to carry out under 550 ℃ air atmosphere.Its activity settled out substantially after adsorbent carried out 4 circulations of reaction regeneration, and the sulfur content after stablizing with adsorbent in the product gasoline is represented the activity of adsorbent, and sulfur content is as shown in table 2 in the product gasoline of stable back.Simultaneously reacted adsorbent is carried out analysis of sulfur content, the results are shown in Table 2.
The intensity of the different adsorbents of table 1 before and after sulfuration
| Adsorbent | ??A1 | ??A2 | ??A3 | ??A4 | ??B1 | ??B2 | ??B3 |
| Abrasion index (fresh dose) | ??7.7 | ??5.7 | ??8.1 | ??5.7 | ??7.7 | ??5.7 | ??8.3 |
| Abrasion index (after the vulcanizing treatment) | ??8.5 | ??6.4 | ??8.6 | ??5.9 | ??13.2 | ??8.9 | ??14.3 |
The adsorption desulfurize performance of the different adsorbents of table 2
| ??A1 | ??A2 | ??A3 | ??A4 | ??B1 | ??B2 | ??B3 | |
| Sulfur content/ppm in the product gasoline | ??31 | ??45 | ??45 | ??43 | ??29 | ??42 | ??46 |
| Sulfur content/wt.% on the adsorbent | ??10.3 | ??9.3 | ??9.3 | ??9.4 | ??10.4 | ??9.3 | ??9.2 |
| ??RON | ??92.4 | ??92.3 | ??92.4 | ??92.3 | ??92.3 | ??92.3 | ??92.4 |
| ??MON | ??82.1 | ??82.1 | ??82.1 | ??82.1 | ??81.6 | ??81.7 | ??81.5 |
| ??Δ(RON+MON)/2 | ??0.1 | ??0.15 | ??0.1 | ??0.15 | ??0.4 | ??0.35 | ??0.4 |
The sulfur content of feed gasoline is 645ppm, and RON is 92.4, and MON is 82.3
Claims (25)
1. a desulfuration adsorbent is a benchmark with the adsorbent gross weight, comprises following composition:
1) aluminium oxide, content are 5-35wt%;
2) silica, content are 3-30wt%;
3) at least a metal oxide that is selected from II B, VB and group vib, content is 10-80wt%;
4) at least a promoter metals that is selected from VIIB and VIII family, content is 3-30wt%;
5) at least a IIA family metal oxide, content is 0.5-10wt%.
2. according to the described adsorbent of claim 1, it is characterized in that, the content of aluminium oxide is 10-25wt%, the content of silica is 10-20wt%, the content that is selected from the metal oxide of II B, VB and group vib is 35-65wt%, the content of promoter metals is 8-20wt%, and IIA family metal oxide content is 1-5wt%.
3. according to the described adsorbent of claim 1, it is characterized in that at least a oxide that is selected from vanadium, zinc or molybdenum element of the metal oxide of the described II of being selected from B, VB and group vib.
4. according to the described adsorbent of claim 1, it is characterized in that at least a metal that is selected from cobalt, nickel, iron and the manganese of described promoter metals.
5. according to the described adsorbent of claim 1, it is characterized in that described IIA family metal oxide comprises the oxide of magnesium and/or calcium.
6. the described preparation of adsorbent method of claim 1 comprises:
(1) water, acid are mixed with binding agent, or also with clay, silica source and IIA family metallic compound at least a the mixing, wear out, obtain the acidifying slurries;
(2) clay, silica source and the IIA family metallic compound of adding do not mix the formation carrier mixture with at least a metal oxide that is selected from II B, VB and group vib and in step (1) with above-mentioned acidifying slurries;
(3) make the said mixture moulding, and form carrier after the roasting;
(4) introducing contains the compound that is selected from VIIB and VIII family promoter metals on above-mentioned carrier, and drying and roasting obtains the adsorbent precursor;
(5) above-mentioned adsorbent precursor is reduced under hydrogeneous atmosphere, promoter metals is existed to go back ortho states basically.
7. according to the described preparation method of claim 6, it is characterized in that described silica source is the natural minerals of silica content greater than 70wt%, other component comprises Al
2O
3, K
2Among O, CaO, the MgO one or more.
8. according to claim 6 or 7 described preparation methods, it is characterized in that described silica source is selected from least a in diatomite, Ludox, silicon gel, macropore silicon oxide and the expanded perlite.
9. according to the described preparation method of claim 6, it is characterized in that described clay is selected from one or more in kaolin, rectorite, Yun Mengshi, bentonite, the imvite.
10. according to the described preparation method of claim 6, it is characterized in that described binding agent is the material that can form heat-resistant inorganic oxide after the roasting, wherein heat-resistant inorganic oxide is one or more in aluminium oxide, silica and the amorphous silicon aluminium.
11., it is characterized in that described binding agent is selected from one or more in hydrated alumina, aluminium colloidal sol, boehmite, false boehmite, hibbsite, the amorphous hydroted alumina according to claim 6 or 11 described preparation methods.
12., it is characterized in that clay is 0.2-1.2 with the ratio of the weight of binding agent according to claim 6 or 11 described preparation methods: 1, silica source is 0.5-1.5 with the ratio of the weight of binding agent: 1.
13., it is characterized in that described I IA family metallic compound is selected from one or more in the nitrate, chloride, formates, acetate of IIA family metal according to the described preparation method of claim 6.
14., it is characterized in that the metal oxide of the described II of being selected from B, VB and group vib is at least a in the oxide of vanadium, zinc or molybdenum according to the described preparation method of claim 6.
15., it is characterized in that described promoter metals comprises a kind of metal that is selected from cobalt, nickel, iron and the manganese at least according to the described preparation method of claim 6.
16., it is characterized in that the compound of described promoter metals is at least a in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide that is selected from promoter metals according to claim 6 or 15 described preparation methods.
17., it is characterized in that according to the described preparation method of claim 6, in step (1), water, acid, binding agent and silica source and clay are mixed, aging, form the acidifying slurries; In step (2), in above-mentioned slurries, add metal oxide and the IIA family metallic compound that is selected from II B, VB and the group vib, form carrier mixture.
18., it is characterized in that according to the described preparation method of claim 6, in step (1), water, acid, binding agent and clay are mixed, aging, form the acidifying slurries; In step (2), in the acidifying slurries, add at least a II B, VB and group vib metal oxide and the pretreated silica source of being selected from, form carrier mixture, wherein pretreated silica source is silica source and IIA family metallic compound mixes and descend the oven dry roasting to obtain at 400-600 ℃.
19. according to claim 6,17 or 18 described preparation methods, it is characterized in that in the step (1), described acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, the consumption of acid makes the pH value of slurries be 1-5, and it is 10-20wt% that the consumption of water makes the concentration of slurries.
20., it is characterized in that in the step (1), aging temperature is generally 60-80 ℃ according to claim 6,17 or 18 described preparation methods, the general 1-3 of ageing time hour.
21. according to the described preparation method of claim 6, it is characterized in that, in the step (3), carrier mixture is the slurries form, and the solid content of slurries is 10-50wt%, and forming granularity by spray-drying is the microballoon of 20-200 micron, in room temperature-400 ℃ drying, 500-800 ℃ of roasting.
22., it is characterized in that according to the described preparation method of claim 6, in the step (4), adopt the method for dipping or precipitation on carrier, to introduce promoter metals, under about 50-300 ℃ temperature, carry out drying, under about 300-800 ℃ temperature, carry out roasting.
23. according to the described preparation method of claim 6, it is characterized in that, in the step (5), the adsorbent precursor reduced under 300-600 ℃ of hydrogeneous atmosphere.
24. the sulfur method of cracking gasoline or diesel fuel is included under 350-500 ℃, and the sulfur-bearing raw material is fully contacted with the described adsorbent of claim 1-5, collects the product that sulfur content reduces.
25., it is characterized in that said contact is carried out according to the described sulfur method of claim 24 in fluid bed.
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| CN 200810246691 CN101766985B (en) | 2008-12-31 | 2008-12-31 | Desulfurizing sorbent and preparation method and application thereof |
| PCT/CN2009/001592 WO2010075672A1 (en) | 2008-12-31 | 2009-12-30 | Desulfurizing adsorbent and preparation method and use thereof |
| JP2011543965A JP5443510B2 (en) | 2008-12-31 | 2009-12-30 | Desulfurizing adsorbent, preparation method, and method of use thereof |
| US13/142,946 US8975208B2 (en) | 2008-12-31 | 2009-12-30 | Desulfurizing adsorbent, preparing process and use thereof |
| BRPI0923919-7A BRPI0923919B1 (en) | 2008-12-31 | 2009-12-30 | DESULFURIZING ADSORBENT, PREPARATION AND USE PROCESS |
| RU2011131329/05A RU2517639C2 (en) | 2008-12-31 | 2009-12-30 | Adsorbent, method for production thereof and method of removing sulphur from cracked petrol or diesel fuel |
| SA110310032A SA110310032B1 (en) | 2008-12-31 | 2010-01-02 | Desulfurizing Adsorbent, Preparing Process and Use Thereof |
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