CN102114405B - Desulfurizing and adsorption agent containing titanium, preparation method and application thereof - Google Patents
Desulfurizing and adsorption agent containing titanium, preparation method and application thereof Download PDFInfo
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Abstract
A desulfurizing and adsorption agent for sulfur removing of cracked gasoline and diesel engine fuel comprises the following compositions of: 1) cleaved muscovite, 2) titanium dioxide binder, 3) oxides of one or more metals chosen from groups IIB, VB and VIB, and 4) at least one metal promoter chosen from cobalt, nickel, iron, and manganese. The adsorption agent possesses good abrasion resistance and desulfurizing activity, can be used for removing the element sulfur and sulfides such as hydrogen sulfide and organic sulfur compound from cracking gasoline and diesel engine fuel.
Description
Technical field
The present invention relates to adsorbent of desulfurization from the liquid charging stock of cracking gasoline and diesel fuel and its preparation method and application.
Background technology
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 that reduces gasoline and diesel oil is considered to one of most important measure that improves air quality, because the sulphur in fuel can produce adverse influence to the performance of vehicle catalytic converter.The sulfur oxide that exists in automobile engine tail gas can suppress the noble metal catalyst in converter and can make it to occur irreversibly poisoning.The gas of discharging from poor efficiency or poisoning converter contains unburned non-methane hydrocarbon and nitrogen oxide and carbon monoxide, and these discharging gas are easily formed photochemical fog by the day photocatalysis.
Most sulphur comes from hot-working petroleum in China's gasoline, is mainly catalytically cracked gasoline, so in cracking gasoline, the minimizing of sulfur content helps to reduce the sulfur content of these gasoline.The existing gasoline products standard of China is GB 17930-2006 " motor petrol ", and this standard further restricts sulfur content in gasoline, requires on December 31st, 2009, and sulfur content in gasoline drops to 50ppm.In this case, catalytically cracked gasoline must just can meet the requirement of environmental protection through deep desulfuration.
In order to guarantee the combustibility of motor vehicle fuel, in the sulfur content that reduces motor vehicle fuel, thereby also should avoid its olefin(e) centent to change as far as possible, its octane number (comprising ROM and MON) is reduced.Generally to cause simultaneously hydrogenation reaction and cause owing to removing thiophenes (comprising thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and methyldibenzothiophene) to the negative effect of olefin(e) centent.In addition, the aromatic hydrocarbons that also needs to avoid described condition to make cracking gasoline also 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 need a kind of in the situation that do not consume in a large number the method for hydrogen desulfurization, thereby process the more economical method that provides for cracking gasoline and diesel fuel.
The method of fixed bed is often adopted in desulfurization from liquid state traditionally, but the reaction uniformity of the method and regeneration all have obvious inferior position.Compare fluidized-bed process with fixed-bed process and have advantages of the aspects such as better heat transfer and pressure drop, therefore have broad application prospects.Fluidized-bed reactor is general adopts granular reactant, but for the great majority reaction, reactant used does not generally have enough wearabilities.Therefore, find anti-wear performance well to have simultaneously the adsorbent of better desulfurization performance significant.
CN 115133A provides a kind of novel absorbing composition that contains zinc oxide, silica, colloidal oxide and promoter, and the preparation method of this adsorbent is provided.But the method adopts the way of pressure forming to prepare the particle of fluidisation, simultaneously by adding pore creating material inflammable when heating to improve its pore volume toward colloid in.The particle that the method is prepared is larger, is the 100-300 micron, and this is not best for fluid mapper process.
The adsorbent of introducing in US 6150300 is: the granular adsorbent composition that comprises the mixture of zinc oxide, silica, aluminium oxide, reduction valence state nickel or cobalt; Its preparation method is mainly to adopt the method such as shearings that silica, aluminium oxide and zinc oxide are mixed and prepares solid particle by comminutor, makes adsorbent thereby flood nickel after drying and roasting.Although the adsorbent of these patent Introductions has desulfurization performance preferably, for its physical and chemical performance, be mainly that tear strength is not introduced in patent.
Adopt promoter metals such as cobalt and nickel dipping to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide in CN 1208124C, reduction accelerator under suitable temperature then is for the preparation of the adsorbent that removes the cracking gasoline medium sulphide content.Improve the abrasion resistance properties of adsorbent by zinc oxide content and binding agent (being mainly the aluminium oxide of the Condea Disperal of company and Vista Dispal) in the adjusting adsorbent.In CN 1627988A, these 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.Describe adsorbent and its preparation method of similar composition in detail in CN 1856359A, CN 1871063A.
By adding clay to improve the intensity of adsorbent, but because clay itself does not have the hole, easily make the pore volume of adsorbent less than normal in these absorbent preparation methods, make the activity decreased of adsorbent.What adopt simultaneously is alumina binder, has zinc aluminate to generate in preparation process, thereby reduces desulphurizing activated.Thereby, be desirable to provide a kind of novel sorbents composition that can be used for removing sulphur from cracking gasoline and diesel fuel, and the preparation method of this adsorbent is provided.
Summary of the invention
The invention provides a kind ofly for remove the adsorbent of sulphur from cracking gasoline and diesel fuel, this adsorbent has good abrasion strength resistance and desulphurizing activated.Compare with existing adsorbent, feature the most significant of this adsorbent is that activity stability is high.
The present invention also provides the preparation method of above-mentioned adsorbent.
The present invention also provides the application of above-mentioned adsorbent.
The present invention is based on following discovery: the mica after employing new material cleavage, the adsorbing agent carrier that comprises zinc oxide, mica and metal oxide binder by formation, thus the service life that a kind of carrier component with fine abrasion strength resistance extends adsorbent can be produced; And adopt novel titanium dioxide binding agent, can avoid the generation of zinc aluminate, thereby increase adsorbent activity.
Adsorbent provided by the invention take the adsorbent gross weight as benchmark, comprises following composition at least:
1) contain at least the silica source of mica, content is 5-40wt%,
2) titanium dioxide binding agent, content are 3-35wt%,
3) at least a oxide that is selected from the metal in IIB, VB and VIB, content is 10-80wt%,
4) at least a promoter metals that is selected from cobalt, nickel, iron and manganese, content is 5-30wt%.
Under preferable case, the content that contains the silica source of mica is 10-30wt%, the content of titanium dioxide binding agent is 8-25wt%, the content that is selected from least a metal oxide in IIB, VB and VIB is 25-70wt%, and the content that is selected from the promoter metals of cobalt, nickel, iron and manganese is 8-25wt%.
More preferably in situation, the content that contains the silica source of mica is 15-27wt%, the content of titanium dioxide binding agent is 10-15wt%, the content that is selected from least a metal oxide in IIB, VB and VIB is 40-60wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 12-20wt%.
Described mica is the mica after cleavage.Mica is phyllosilicate, is to clip by two-layer silicon-oxy tetrahedron the compound silica layer that one deck alumina octahedral consists of, and its basic structure is [AlSi
3O
10] the silicon-oxy tetrahedron structure, one of them Si
4+By Al
3+Get and replace.Cleavage is mica completely, can be split into sheet as thin as a wafer, and sheet is thick to be reached below 1 μ m.Its chemical constitution is:
AB
2[AlSi
3O
10]·(OH)
2
Wherein A represents K, Na and/or Li; B represents Al and/or Fe.
Described mica can be divided into muscovite, phlogopite, emerylite, phlogopite, biotite etc., the muscovite after the preferred cleavage of the present invention according to the difference of color and luster and pattern.It is little that muscovite has a natural particle diameter, easily the characteristics of processing superfine; Its chemical composition, structure, structure and kaolin are close, have again some characteristic of clay mineral, and namely dispersion suspension is good in aqueous medium and organic solvent, the advantages such as toughness.Its general chemical composition (quality) is: SiO
2Content is 44.9～50.3%, Al
2O
3Content is 27.9～39.5%; M
2O content is 8.9～10.1% (M is the IA compounds of group), H
2O content is 4.2～6.2%, contains in addition a small amount of or micro Fe
2O
3, Mn
2O
3, CaO etc.
In adsorbent of the present invention except mica, can also contain other silica source, as one or more in clay (comprising kaolin, laminated clay column etc.), diatomite, Ludox, silicon gel, macropore silicon oxide and expanded perlite etc., the quality of other silica source is no more than 4: 1 with the ratio of mica quality, preferably be no more than 2: 1, more preferably no more than 1: 1.
The described oxide that is selected from one or more metals in IIB, VB and VIB, one or more in preferential oxidation vanadium, zinc oxide or molybdenum oxide, most preferably zinc oxide.
Described promoter metals can be reduced to oxidation state sulphur the metal of hydrogen sulfide for any.This promoter component comprises one or more metals that are selected from cobalt, nickel, iron and manganese at least, and preferred promoter metals contains nickel.
According to a further aspect in the invention, provide a kind of preparation method of sorbent systems, comprising:
(1) the titanium dioxide precursor is hydrolyzed in acidic liquid, forms colloidal sol;
(2) make the colloidal sol of (1) and the silica source that contains at least mica and be selected from IIB, VB and contact with one or more metal oxides in VIB, form carrier mixture; Dry, roasting obtain carrier;
(3) introduce the compound that contains promoter metals in the carrier of (2), obtain the adsorbent precursor;
(4) the adsorbent precursor in drying, roasting (3);
(5) the adsorbent precursor after roasting is reduced under hydrogen atmosphere, obtain adsorbent.
In step (1), described titanium dioxide precursor is the compound that can exist with the anatase titanium dioxide form after hydrolysis, roasting in acidic liquid, one or more in preferred titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.Still can generate anatase titanium dioxide after wherein anatase titanium dioxide hydrolysis, roasting.The titanium dioxide precursor contacts with excess acid solution, can be hydrolyzed and generate caking property colloidal solution.
Described acidic liquid can be acid or aqueous acid, and said acid is selected from one or more in water-soluble inorganic acid and/or organic acid, is preferably one or more in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.The consumption of acid makes the pH value of slurries for 1-5, is preferably 1.5-4.
In step (2), the colloidal sol of step (1) and the silica source that contains at least mica and one or more metal oxides of being selected from IIB, VB and VIB are mixed.Can directly add silica source and metal oxide powder in colloidal sol, also can be respectively or add simultaneously the slurries that contain silica source and metal oxide that prepare in advance.
The resulting carrier mixture of step (2) can be the forms such as wet mixture, dough, pastel or slurries, then makes the gained 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, then length make the extrudate of gained carry out drying, roasting at the cylindrical extrudate of 2.0-5.0mm.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, forms by spray-drying the microballoon that granularity is the 20-200 micron, reaches the purpose of moulding.For the ease of spray-drying, the solid content of dry front slurries is 10-50wt.%, is preferably 20-50wt.%.
The drying means of carrier mixture and condition are conventionally known to one of skill in the art, for example dry method can be dry, oven dry, forced air drying.Dry temperature can be room temperature to 400 ℃, is preferably 100-350 ℃.
The roasting condition of carrier mixture is also conventionally known to one of skill in the art, and in general, sintering temperature is 400-700 ℃, is preferably 450-650 ℃, and roasting time is at least 0.5 hour, is preferably 0.5-100 hour, more preferably 0.5-10 hour.
In step (3), can adopt the method that well known to a person skilled in the art dipping or precipitation to introduce metallic promoter agent on carrier.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, then adds ammoniacal liquor will contain the compound precipitation of promoter metals on carrier.The described compound that contains promoter metals is to be converted into the material of promoter metals oxide under calcination condition, can be selected from acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of promoter metals, and two or more mixture etc. wherein.Described promoter metals preferably contains nickel.
In step (4), the carrier of introducing promoter component is approximately under 50-300 ℃, carries out drying under preferred 100-250 ℃, is about 0.5-8 hour drying time, more preferably from about 1-5 hour.After drying, under the condition that has oxygen or oxygen-containing gas to exist approximately 300-800 ℃, more preferably carry out roasting at the temperature of 450-750 ℃, general approximately 0.5-4 of needed time of roasting hour, preferred 1-3 hour, until volatile materials is removed and promoter metals is converted into metal oxide, obtain the adsorbent precursor.
In step (5), the adsorbent precursor is reduced under 300-600 ℃ of hydrogeneous atmosphere, promoter metals is existed with reduction-state 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, comprising: the sulfur-bearing raw material is fully contacted under hydrogen atmosphere with adsorbent of the present invention, and the temperature and pressure condition is: 350-500 ℃, and 0.5-4MPa; Preferred 400-450 ℃, 1.0-2.0MPa.Sulphur in this process Raw is adsorbed on adsorbent, thereby obtains gasoline or the diesel fuel of low sulfur content.
Can reuse after reacted adsorbent reactivation.Regenerative process is carried out under oxygen atmosphere, and regeneration condition is normal pressure, and temperature is 400-700 ℃, preferred 500-600 ℃.
After regeneration, adsorbent also need to reduce under hydrogen atmosphere before reusing, and the temperature and pressure scope of reduction is: 350-500 ℃, and 0.2-2MPa; Preferred 400-450 ℃, 0.2-1.5MPa.
It is hydrocarbon or its any cut of 40 ℃ to 210 ℃ that term used herein " cracking gasoline " means boiling range, is from making larger hydrocarbon molecule be cracked into the product of more micromolecular heat or catalytic process.Applicable thermal cracking process includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of applicable catalytic cracking process includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, applicable catalytically cracked gasoline 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 with described cracking gasoline fractionation and/or hydrotreatment before desulfurization during in some cases, in the methods of the invention as hydrocarbon-containifluids fluids.
It is the hydrocarbon mixture of 170 ℃ to 450 ℃ 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.
Term used herein " sulphur " represents the normal organosulfur compound that exists in any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel fuel.The sulphur that exists in 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 methyldibenzothiophene, and the normal larger thiophenes of molecular weight that exists in diesel fuel.
Adsorbent provided by the invention has very high abrasion strength resistance and larger pore volume, rareer is that this adsorbent in use keeps very high activity stability, be very suitable for the adsorption desulfurize process in fluidized-bed reactor, and have extraordinary service life.
Description of drawings
Fig. 1 is muscovite crystal structure schematic diagram.It (is Al for muscovite by cationic layer that is octahedral coordination of folder between two identical silicon-oxy tetrahedrons [(Si, Al) O4] stratum reticulare
3+) form, each tetrahedral drift angle oxygen and the shared oxygen of three adjacent octahedral drift angles are due to Al
3+Only occupy two in three octahedral interstices, be dioctahedron type mica.This has just consisted of by two-layer six side's stratum reticulares and has been sandwiched in the structure sheaf that one deck octahedron therebetween forms.Si in six side's stratum reticulares of muscovite
4+Have 1/4th by Al
3+Replace, residual charge occurs in whole mica structure sheaf, thereby have than macrocation (K between the mica structure sheaf
+) exist with balancing charge.
Fig. 2 is the X-ray diffraction pattern of muscovite, and there is stronger peak (characteristic peak) at the crystalline phase peak of muscovite at 9 ° and 27 °, can be used for distinguishing this system adsorbent.The test of XRD is carried out on the German Siemens D5005 of company type X-ray diffractometer, Cu target, K
αRadiation, solid probe, tube voltage 40kV, tube current 40mA.
Fig. 3 is the XRD spectra of adsorbent A 1 precursor of embodiment 1 preparation.Come as seen from Figure 3 the crystalline phase of adsorbent A 1 precursor to mainly contain zinc oxide, nickel oxide, muscovite and titanium dioxide composition.The corresponding relation of each component on XRD figure is 1: muscovite; 2:TiO
23:ZnO; 4:NiO.
The specific embodiment
The present invention is described further for following example, but therefore do not limit the present invention.
Desulfurized effect is weighed with the product sulfur content, and in product, sulfur content adopts the off-line chromatography, and the composition of adsorbent adopts X-ray diffraction (XRD) analysis.
Embodiment 1
With 3.36 kilograms of titanium tetrachlorides (Beijing Chemical Plant, analyze pure, 99%) slowly join in 3.2 kilograms of deionized waters, and slowly stir and avoid the titanium oxide crystal to separate out, this moment, solution was water white colloidal solution state, was called titanium colloidal sol.
5.55 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, and contains 5.38 kilograms of butts) and 10.8 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes; Add the mica (containing 1.84 kilograms of butts) of 2.11 kilograms in the zinc oxide slurries, and mix 15 minutes.Then join in above-mentioned titanium colloidal sol, stir and obtained the carrier mixture slurries in 1 hour.
Described carrier pulp adopts Niro Bowen Nozzle Tower
TMThe spray dryer of model carries out spray-drying, and spray-drying pressure is 8.5 to 9.5MPa, and inlet temperature is below 500 ℃, and outlet temperature is about 150 ℃.Then the microballoon that is obtained by spray-drying first under 180 ℃ dry 1 hour obtained adsorbing agent carrier in 1 hour 635 ℃ of lower roastings.
The adsorbing agent carriers of 3.24 kilograms (3.0 kilograms of butts) are flooded with 2.38 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 635 ℃ of roastings of air atmosphere through 180 ℃ of dryings.Adsorbent precursor reductase 12 in the hydrogen atmosphere of 425 ℃ hour can obtain adsorbent, and the nickel oxide in this moment precursor is reduced to metallic nickel.This adsorbent is designated as adsorbent A 1.
The main chemical composition of adsorbent A 1 is: zinc oxide content is 53.8wt%, and the content of titanium dioxide is 14.0wt%, and muscovite content is 18.4wt%, and nickel (calculating take metallic nickel) is as 13.8wt%.
With 3.09 kilograms of tetraethyl titanates (Aldrich company, analyze pure, 99%) in the situation that in stirring nitric acid (chemical pure, the Beijing Chemical Plant produces) solution slowly join 3.2 kilogram 10% and stirred 1 hour, this moment, solution was faint yellow transparent colloidal solution, was called titanium colloidal sol.
The mica of 4.88 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, contain 4.73 kilograms of butts) and 3.01 kilograms is joined (containing 2.62 kilograms of butts) in the deionized water of 10.8 kilograms, and mix 30 minutes.Then add the tetraethyl titanate after said hydrolyzed, stir after mixing and obtaining the carrier mixture slurries in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtaining adsorbent A 2.The main chemical composition of adsorbent A 2 is: zinc oxide content is 47.3wt%, and the content of titanium dioxide is 10.7wt%, and muscovite content is 26.2wt%, and nickel (calculating take metallic nickel) is as 15.8wt%.
With 1.51 kilograms of titanium dioxide (Detitanium-ore-types, contain 1.40 kilograms of titanium dioxide butts) join the hydrochloric acid (chemical pure of 3.6 kilogram 30%, the Beijing Chemical Plant produces) in and stirred acidifying 1 hour, this moment, titanium oxide was dissolved as water white colloidal solution fully, was called titanium colloidal sol.
5.55 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, and contains 5.38 kilograms of butts) and 10.8 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes; Add muscovite (containing 1.20 kilograms of butts) and 0.67 kilogram of expanded perlite (containing 0.64 kilogram of butt) of 1.38 kilograms in the zinc oxide slurries, and mix 15 minutes.Then add above-mentioned titanium colloidal sol, stir after mixing and obtained the carrier mixture slurries in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtaining adsorbent A 3.The main chemical composition of adsorbent A 3 is: zinc oxide content is 53.8wt%, and the content of titanium dioxide is 14.0wt%, and muscovite content is 12.0wt%, and expanded perlite content is 6.4wt%, and nickel (calculating take metallic nickel) is as 13.8wt%.
Comparative Examples 1
This Comparative Examples adopts aluminium oxide as binding agent.
5.55 kilograms of Zinc oxide powders (Beijing Chemical Plant produces, and contains 5.38 kilograms of butts) and 10.8 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes.
(Shandong Aluminum Plant produces to get 1.91 kilograms, aluminium oxide, contain 1.4 kilograms of butts) and the rectorite (containing 1.84 kilograms of butts) of 2.46 kilograms under agitation mix, then after adding 4.0 kilograms of deionized waters to mix, add the hydrochloric acid (chemical pure, Beijing Chemical Plant produce) of 400 milliliter 30% stir acidifying be warming up to after 1 hour 80 ℃ aging 2 hours.Stir after adding again above-mentioned zinc oxide slurries to mix and obtained carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtaining adsorbent B 1.The main chemical composition of adsorbent B 1 is: zinc oxide content is 53.8wt%, and the alumina bound agent content is 14.0wt%, and rectorite content is 18.4wt%, and nickel (calculating take metallic nickel) is as 13.8wt%.
Comparative Examples 2
This Comparative Examples adopts aluminium oxide as binding agent.
The rectorite of 4.88 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, contain 4.73 kilograms of butts) and 3.50 kilograms is joined (containing 2.62 kilograms of butts) in the deionized water of 11.8 kilograms, and mix 30 minutes and obtain mixed serum.
Get 1.46 kilograms of monohydrate aluminas (the SB powder contains 1.07 kilograms of butts) and join in 3.6 kilograms of deionized waters, and stirred 10 minutes; Then add the nitric acid (chemical pure, the Beijing Chemical Plant produces) of 350 milliliter 30% to stir acidifying 1 hour.Add again above-mentioned zinc oxide and rectorite slurries, stir after mixing and obtained carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtaining adsorbent B 2.The main chemical composition of adsorbent B 2 is: zinc oxide content is 47.3wt%, and the alumina bound agent content is 10.7wt%, and rectorite content is 26.2wt%, and nickel (calculating take metallic nickel) is as 15.8wt%.
Comparative Examples 3
(Shandong Aluminum Plant produces to get 1.91 kilograms, aluminium oxide, contain 1.4 kilograms of butts) and after 4.0 kilograms of ionized waters mix, adding the hydrochloric acid (chemical pure, Beijing Chemical Plant produce) of 360 milliliter 30% to stir acidifying is warming up to 80 ℃ and drops to room temperature after aging 2 hours after 1 hour.
With the expanded perlite of 5.55 kilograms of Zinc oxide powders (Beijing Chemical Plant produce, contain 5.38 kilograms of butts) and 1.89 kilograms (contain 1.84 kilograms of butts, silica content 72wt%, alumina content 19wt.%, all the other are CaO, Fe
2O
3, the impurity such as MgO) join in the deionized water of 10.8 kilograms, and mix 30 minutes.Then add above-mentioned alumina sol, stir after mixing and obtained carrier pulp in 1 hour.
Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtaining adsorbent B 3.The main chemical composition of adsorbent B 3 is: zinc oxide content is 53.8wt%, and the alumina bound agent content is 14.0wt%, and expanded perlite content is 18.4wt%, and nickel (calculating take metallic nickel) is as 13.8wt%.
Investigate abrasion strength resistance and two indexs of desulfurization performance to adopting the adsorbent that distinct methods is prepared.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 Engineering Analysis method (RIPP) experimental technique ", and numerical value is less, shows that abrasion strength resistance is higher.Different adsorbent attrition evaluation results are as shown in table 1.
In order to investigate the performance of adsorbent, the crystalline phase of A1, A2, B1-B3 forms to be analyzed.Crystal phase analysis adopts X-ray diffraction and phase filtering (R.V.Siriwardane, J.A.Poston, G.Evans, Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), Rietveld model (RIQAS rietveld Analysis, the operation manual through revising, Material Data, Inc., Berkley, CA (1999)), analyze different samples, and the method for employing match calculates the crystalline phase composition of sample.Use is equipped with the Philips XRG3100 generator of the long fine focusing copper X-ray source that drives with 40kV, 30mA; Philips3020 digital angle measurement instrument and Philips3710MPD control computer; Carrying out all X-ray diffractions with the cooling silicon detector of Kevex PSI Peltier measures.Adopt Kevex 4601 ionic pump controllers, Kevex4608Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A single channel analyzer operation Kevex detector.Use Philips APD 4.1c version software to obtain diffraction pattern.Use Material Data, Inc.Riqas 3.1c version software (Outokumpu HSCChemistry for Windows: user's manual, Outokumpo Resarch Oy, Pori, Finland (1999)) carries out all rietveld and calculates.The zinc aluminate content of different adsorbents is as shown in table 1.
Adopt simultaneously following methods that the desulfurization performance of these adsorbents is estimated.Desulfurized effect is weighed with the product sulfur content, and in product, sulfur content adopts the off-line chromatography.The adsorbent desulfurization performance adopts the little anti-experimental provision of fixed bed to estimate, and it is the catalytically cracked gasoline of 1080ppm 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, adsorbent processings of regenerating after reaction is completed, the regeneration processing is what to carry out under the air atmosphere of 550 ℃.After adsorbent carries out 6 circulations of reaction regeneration, its activity settles out substantially, represents the activity of adsorbent with the sulfur content in the stable rear product gasoline of adsorbent, and in stable rear product gasoline, sulfur content is as shown in table 2.Simultaneously reacted adsorbent is carried out analysis of sulfur content, the results are shown in Table 2.
The tear strength of the different adsorbents of table 1 and zinc aluminate content
| Adsorbent | A1 | A2 | A3 | B1 | B2 | B3 |
| Abrasion index | 6.4 | 4.9 | 7.9 | 6.8 | 5.1 | 8.6 |
| ZnAl 2O 4％ | 0 | 0 | 0 | 10.5 | 8.7 | 9.2 |
The intensity of the different adsorbents of table 2 and adsorption desulfurize performance
| A1 | A2 | A3 | B1 | B2 | B3 | |
| Sulfur content/ppm in |
30 | 31 | 34 | 76 | 78 | 78 |
| Δ(RON+MON)/2 | 0.35 | 0.5 | 0.4 | 0.4 | 0.5 | 0.45 |
Annotate: the sulfur content of feed gasoline is 1080ppm, and RON is that 93.1, MON is 82.7
Can find out from table 1 and 2, adsorbent of the present invention has good tear strength and desulphurizing activated simultaneously.
Claims (17)
1. desulfuration adsorbent take the adsorbent gross weight as benchmark, comprises following composition at least:
1) contain at least the silica source of mica, content is 5-40wt%,
2) titanium dioxide binding agent, content are 3-35wt%,
3) at least a oxide that is selected from the metal in IIB, VB and VIB, content is 10-80wt%,
4) at least a promoter metals that is selected from cobalt, nickel, iron and manganese, content is 5-30wt%.
2. according to adsorbent claimed in claim 1, it is characterized in that, the content that contains the silica source of mica is 10-30wt%, the content of titanium dioxide binding agent is 8-25wt%, the content that is selected from least a metal oxide in IIB, VB and VIB is 25-70wt%, and the content that is selected from the promoter metals of cobalt, nickel, iron and manganese is 8-25wt%.
3. according to adsorbent claimed in claim 1, it is characterized in that, the content that contains the silica source of mica is 15-27wt%, the content of titanium dioxide binding agent is 10-15wt%, the content that is selected from least a metal oxide in IIB, VB and VIB is 40-60wt%, and the content that is selected from the promoter metals of cobalt, nickel, iron and manganese is 12-20wt%.
4. according to adsorbent claimed in claim 1, it is characterized in that, described mica is the muscovite after cleavage.
5. according to adsorbent claimed in claim 1, it is characterized in that, in silica source except mica, contain one or more other silica source that are selected from clay, diatomite, Ludox, silicon gel, macropore silicon oxide and expanded perlite, the quality of other silica source is no more than 4: 1 with the ratio of mica quality.
6. according to adsorbent claimed in claim 1, it is characterized in that, the oxide of the metal in the described IIB of being selected from, VB and VIB is one or more in vanadium oxide, zinc oxide or molybdenum oxide.
7. according to adsorbent claimed in claim 1, it is characterized in that, contain nickel in described promoter metals.
8. the preparation method of the described adsorbent of claim 1 comprises:
(1) the titanium dioxide precursor is hydrolyzed in acidic liquid, forms colloidal sol;
(2) make the colloidal sol of (1) and the silica source that contains at least mica and be selected from IIB, VB and contact with one or more metal oxides in VIB, form carrier mixture; Dry, roasting obtain carrier;
(3) introduce the compound that contains promoter metals in the carrier of (2), obtain the adsorbent precursor;
(4) the adsorbent precursor in drying, roasting (3);
(5) the adsorbent precursor after roasting is reduced under hydrogen atmosphere, obtain adsorbent.
9. according to preparation method claimed in claim 8, it is characterized in that, in step (1), described titanium dioxide precursor is the compound that can exist with the anatase titanium dioxide form after hydrolysis, roasting in acidic liquid.
10. according to preparation method claimed in claim 8, it is characterized in that, described titanium dioxide precursor is selected from one or more in titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
11. according to preparation method claimed in claim 8, it is characterized in that, in step (1), the consumption of acid makes the pH value of colloidal sol be 1-5.
12. according to preparation method claimed in claim 8, it is characterized in that, in step (2), dry temperature is room temperature to 400 ℃, sintering temperature is 400-700 ℃, and roasting time is at least 0.5 hour.
13. according to preparation method claimed in claim 8, it is characterized in that, in step (3), adopt the method for dipping or precipitation to introduce the compound that contains promoter metals on carrier.
14. according to the described preparation method of claim 13, it is characterized in that, the described compound that contains promoter metals is selected from one or more in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of promoter metals.
15. according to preparation method claimed in claim 8, it is characterized in that, in step (4), introduce the carrier of promoter component after drying under 50-300 ℃, carry out roasting at 300-800 ℃ of temperature under the condition that oxygen-containing gas exists.
16. according to preparation method claimed in claim 8, it is characterized in that, in step (5), the adsorbent precursor reduced under 300-600 ℃ of hydrogeneous atmosphere.
17. the sulfur method of a cracking gasoline or diesel fuel, comprise: make one of sulfur-bearing raw material and claim 1-7 described adsorbent under hydrogen atmosphere, 350-500 ℃ with the 0.5-4MPa condition under fully contact, obtain gasoline or the diesel fuel of low sulfur content.
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| CN1355727A (en) * | 1999-08-25 | 2002-06-26 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN1519297A (en) * | 2003-01-24 | 2004-08-11 | 中国石油化工股份有限公司 | Adsorbent for desulfurizing fuel oil and preparation method |
| CN1552802A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Cracking assistants with desulfurizing function and preparing method thereof |
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| CN1355727A (en) * | 1999-08-25 | 2002-06-26 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN1519297A (en) * | 2003-01-24 | 2004-08-11 | 中国石油化工股份有限公司 | Adsorbent for desulfurizing fuel oil and preparation method |
| CN1552802A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Cracking assistants with desulfurizing function and preparing method thereof |
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