CN104209142A - Hydrocarbon oil desulfurization catalyst and application method thereof - Google Patents
Hydrocarbon oil desulfurization catalyst and application method thereof Download PDFInfo
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Abstract
The invention relates to a hydrocarbon oil desulfurization catalyst and an application method thereof. The catalyst contains a gallium modified ultrastable Y type molecular sieve and a metal oxide with a sulfur adsorption function. In the molecular sieve, the molar ratio of silicon-aluminum atoms is 3.5-25, and the mole ratio of silicon-gallium atoms is 4-90. The weight ratio of the molecular sieve to the metal oxide with the sulfur adsorption function is 15-98:2-85. The desulfurization catalyst provided by the invention can be used for desulfurization of hydrocarbon oil, and has the advantages of high hydrocarbon oil yield, high desulfurization efficiency, and high gasoline octane number.
Description
Technical field
The present invention relates to and refine hydrocarbon ils with solid, the present invention relates to the desulfurization of hydrocarbon ils furtherly.
Background technology
Sulphur in automobile-used oil product can cause serious atmosphere pollution, various countries have formulated sulfur content in strict standard restriction vehicle fuel for this reason, the GB17930-2006 regulation implemented such as on December 6th, 2006, the sulfur content of motor petrol (II) is not more than 500ppm(mass fraction), the sulfur content of motor petrol (III) is not more than 150ppm(mass fraction).National environmental protection regulation has had stricter restriction to the content of pollutant in product oil in recent years, and the ground such as Beijing and Shanghai takes the lead in state of enforcement IV discharge standard, more requires that sulfur content in gasoline is reduced to 50ppm(mass fraction) below.
At present, the method removing sulphur in automobile-used oil product mainly contains: catalytic desulfurhydrogenation, catalytic cracking and desulfurizing, oxidation sweetening, solvent extraction desulfurization, biological desulphurization, adsorption desulfurize, film desulfurization and photocatalysis desulfurization etc.Wherein adsorption desulfurize is by being adsorbed on the sorbent by the sulfur-containing compounds such as the mercaptan in oil product, disulphide, thioether and thiophene-based, realize the object reducing sulfur content in oil products, having advantage simply, easily and fast, is one of current people's desulfur technology comparing concern.
USP5807475 discloses a kind of method removing sulfur-containing compound from hydrocarbon mixture, by hydrocarbon ils and adsorbent contact at being included in 10 ~ 100 DEG C, is enough to time of contact make the sulfur-containing compound in hydrocarbon ils be adsorbed onto on adsorbent; Described adsorbent is selected from NiX, MoX, NiY zeolite and surface area is at least 150m
2the imvite of/g.
CN1714926 discloses a kind of molecular sieve for removing organic compounds containing sulfur in oil product and method for making thereof.It is the Y molecular sieve that load has copper or nickel, or the MCM-41 molecular sieve containing titanium.For being dissolved in removing of benzothiophene in normal octane, desulfurization degree is higher.
USP6150300 discloses a kind of preparation method of sulfur absorbent, comprises and the component of silicon oxide-containing, the component of containing metal oxide and the component containing zinc oxide being mixed, then this mixture is made the ball of diameter 10 ~ 1000 microns.
The preparation method of sulfur absorbent disclosed in USP6184176, comprises and zinc oxide, silica, aluminium oxide is mixed and made into particle, floods after drying, roasting with cobalt or containing the compound of cobalt, with reducing agent, the cobalt in adsorbent is reduced into zeroth order after drying, roasting.This adsorbent is used for cracking gasoline or cracked diesel oil desulfurization, the temperature of adsorption desulfurize makes cracking gasoline or diesel oil be gaseous state, preferred gasoline absorbing desulfurization temperature is 204 ~ 427 DEG C (400 ~ 800 °F), the temperature of diesel oil adsorption desulfurizing is 260 ~ 487 DEG C (500 ~ 900 °F), and the desulfurizing agent after absorption uses through regeneration and activation Posterior circle.CN 1130253C provides a kind of novel absorbent composition containing zinc oxide, silica, aluminium oxide and nickel or cobalt, and provides the preparation method of this adsorbent.First the method prepares the carrier containing zinc oxide, silica, aluminium oxide, then introduces nickel by dipping.This adsorbent can be used for removing sulphur from cracking gasoline or diesel fuel.
Promoter metals such as cobalt and nickel dipping is adopted to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide in CN 1208124C, then reduction accelerator at appropriate temperatures, for the preparation of the adsorbent removing cracking gasoline medium sulphide content.
While above-mentioned adsorbent removes sulfur in gasoline under hydro condition, inevitably because olefin saturated causes octane number to reduce.
CN 101433821A provides a kind of adsorbent reducing sulfur content in hydrocarbon oils, comprises rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; By above-mentioned rare earth faujasite and carrier mixture preshaped be porous heat-resistant solid particle, then introduce metal active constituent on this solid particle, prepare described adsorbent.
CN 101434854A provides a kind of adsorbent reducing sulfur content of light hydrocarbon oil, comprises P Modification rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; By preshaped with carrier mixture after P Modification for above-mentioned rare earth faujasite be porous heat-resistant solid particle, then introduce metal active constituent on this solid particle, prepare described adsorbent.
Although above-mentioned two pieces patent can improve the octane number of gasoline, can only have good desulfurization and improve octane number effect within the shorter reaction time, the longer routine desulfurization degree of desulfurization time declines, and octane number increase rate is limited, and liquid yield is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst for desulfurization under gasoline high temperature, and this catalyst contains the Y zeolite of gallium modification, can improve the octane number of gasoline.
The invention provides a kind of desulfurization of hydrocarbon oil catalyst, faujasite molecular sieve containing gallium modification and the metal oxide with absorption sulfur functional, the sial atomic molar ratio of described molecular sieve is 3.5 ~ 50, silicon gallium atomic molar ratio is 4 ~ 90, lattice constant is less than 24.6nm, molecular sieve is (15 ~ 98) with the weight ratio with the metal oxide adsorbing sulfur functional: (2 ~ 85), the faujasite of described gallium modification is the super-stable Y molecular sieves mending gallium through framework dealumination, in the skeleton structure of this molecular sieve, gallium instead of the part aluminium in green bone shelf structure, the metal oxide of described absorption sulfur functional comprises zinc oxide.
The invention provides a kind of sulfur method, comprise the step by gasoline and above-mentioned catalyst exposure, the temperature wherein contacted is 200 ~ 500 DEG C, the pressure of contact is 0.1 ~ 1.0MPa, introduce nitrogen in contact, steam, hydrogen, carbon monoxide, carbon dioxide, boiling point are less than the hydrocarbon gas of 0 DEG C and one or more in fluid catalytic cracking dry gas, in atmosphere, this gas proportion is 10 ~ 40 volume %
Desulphurization catalyst provided by the invention, for gasoline desulfur, can within the longer operating time, improve the octane number of gasoline and maintain higher desulfurization of hydrocarbon oil rate, yield of gasoline is high; Described catalyst stability is good, through repeatedly regenerating, can maintain high desulfurization activity and improving octane number ability.Inventive desulfurization method, hydrocarbon ils yield is high, and desulfuration efficiency is high, and octane number improves.Sulfur method provided by the invention, catalyst not only can sulphur in adsorbed gasoline, under the effect of the acid site of molecular sieve, the sulphur of absorption can also be converted into hydrogen sulfide, thus high desulfurization performance can be kept the long period, can desulfurization under no hydrogen existent condition.
Detailed description of the invention
According to catalyst of the present invention, the faujasite molecular sieve of described gallium modification is the super-stable Y molecular sieves mending gallium through framework dealumination, the sial atomic molar of molecular sieve is than being preferably 5 ~ 25, and silicon gallium atomic molar ratio is 4 ~ 90, and the specific area of described molecular sieve is 150 ~ 620m
2/ g, lattice constant is less than 2.46nm, such as, be 2.43 ~ 2.47nm.
Of the present inventionly mend the super-stable Y molecular sieves of gallium through framework dealumination, the present invention is called ［ Ga ］ Y molecular sieve, gallium is positioned in the skeleton structure of molecular sieve, instead of the part aluminium in Y zeolite green bone shelf structure.The described super-stable Y molecular sieves through framework dealumination benefit gallium is the Y zeolite with skeleton gallium atom of secondary synthesis, can prepare according to existing method, such as, according to method preparation disclosed in USP5238675.The described super-stable Y molecular sieves mending gallium through framework dealumination, preferred preparation method is as follows: mixed with ammonium acetate solution by Y zeolite raw material, and break into slurry, slurry is heated to 50 ~ 95 DEG C preferably 70 DEG C ~ 90 DEG C, then, slowly and equably add by Ga (NO
3)
3and NH
4the fluorine gallic acid ammonium salt solution that F is formulated, reaction 3 ~ 10h, product after filtering, uses (NH
4)
2sO
4or NH
4cl solution washing, such as at 65 ~ 95 DEG C, preferably at 80 ~ 90 DEG C, wash 2 ~ 4h, described washing can repeat one or many, to wash away the fluoride in product, namely obtains the Y zeolite of gallium modification after drying, roasting.Described Y zeolite raw material is Si-Al molecular sieve, has sial skeleton structure, and described Y zeolite raw material can be NH
4one or more in Y, HY, USY, REY, REHY, REUSY, the concentration of described ammonium acetate solution can be 0.5 ~ 2.5mol/L, wherein the weight ratio of ammonium acetate solution and Y zeolite raw material can be 5 ~ 20:1 preferably 8 ~ 15:1, describedly slowly and equably adds such as: feed rate be 50 ~ 500mL fluorine gallic acid ammonium salt solution/gram Y zeolite raw material/hour.Described fluorine gallic acid ammonium salt solution can pass through Ga (NO
3)
3, NH
4the method preparation of F and water mixing, wherein Ga (NO
3)
3with NH
4the weight ratio of F is 2 ~ 1:1, Ga (NO in solution
3)
3with NH
4the total content of F is 1 ~ 10 % by weight, and the weight ratio of fluorine gallic acid ammonium salt solution and Y zeolite raw material is 1 ~ 15:1, preferably 2 ~ 12:1.The ammonium chloride of described washing or ammonium sulfate concentration can be 0.5 ~ 3mol/L, and the weight ratio of ammonium sulfate and molecular sieve can be 5 ~ 20:1.
According to catalyst of the present invention, the described metal oxide with absorption sulfur functional is selected from one or more in I A race, II A race, III A race or transition metal oxide, is preferably one or more in the oxide of Na, K, Mg, Ca, Al, lanthanide series metal, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt.The ratio of the described metal oxide and molecular sieve with absorption sulfur functional is (15 ~ 98): (2 ~ 85).
According to catalyst of the present invention, described catalyst comprise 20 ~ 75 % by weight gallium modifications super-stable Y molecular sieves, 22 ~ 60 % by weight zinc oxide, 0 ~ 30 % by weight such as 1 ~ 25 % by weight other have absorption sulfur functional metal oxide; More preferably, described catalyst comprises the super-stable Y molecular sieves of 25 ~ 70 % by weight gallium modifications, the zinc oxide of 25 ~ 55 % by weight, and other of 0 ~ 20 % by weight such as 2 ~ 15 % by weight has the metal oxide adsorbing sulfur functional.The described metal oxide that other has absorption sulfur functional is one or more in the oxide of Na, K, Mg, Ca, Al, lanthanide series metal, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt, is preferably one or more in the oxide of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt.Metal oxide that described other has an absorption sulfur functional be preferably in cobalt oxide, nickel oxide, cupric oxide, molybdenum oxide, aluminium oxide, iron oxide one or more, zinc oxide and the described weight ratio that other has the metal oxide adsorbing sulfur functional are 1 ~ 20:1, be such as 1 ~ 15:1, be preferably 1 ~ 5:1.Described metal oxide is derived from oxide or the oxide precursor of metal, described oxide precursor is preferably the soluble-salt of metal, the nitrate of such as metal, sulfate, chloride, carbonate or acylate, described organic salt is acetate, formates such as.Its average grain diameter of described zinc oxide (diameter) is preferably less than 100nm, such as, be 10 ~ 75nm.
According to catalyst of the present invention, also can contain in al binder, inorganic oxide matrix one or more, take total catalyst weight as benchmark, molecular sieve and the content with absorption sulfur functional metal oxide are 50 ~ 100 % by weight, preferably 60 ~ 99.6 % by weight, and be such as 50 ~ 90 % by weight, 40 % by weight are no more than in the content of aluminium oxide al binder, be such as 5 ~ 35 % by weight, be no more than 40 weight with the content of oxide basis inorganic matter matrix of oxide, be preferably 0 ~ 30 % by weight.Desulphurization catalyst provided by the invention can comprise described super-stable Y molecular sieves, the zinc oxide of 25 ~ 55 % by weight, a kind of VIII family metal oxide, the binding agent of 0 ~ 35 % by weight such as 3 ~ 25 % by weight and the inorganic matter matrix of 0 ~ 20 % by weight such as 1 ~ 15 % by weight that are selected from VIII group 4 transition metal of 3 ~ 25 % by weight of mending gallium through framework dealumination of 30 % by weight ~ 70 % by weight.Described al binder is boehmite and/or Alumina gel.Described inorganic oxide matrix is selected from one or more in aluminium oxide, silica, amorphous aluminum silicide, clay.Described clay is selected from bentonite, galapectite, kaolinite, montmorillonite, mica or palygorskite, the mica-montmorillonite of natural and Prof. Du Yucang, as rectorite, Yun Mengshi, mica-montmorillonite, illite-montmorillonite, glauconite-montmorillonite, chlorite-montmorillonite, mica-vermiculite or kaolinite-montmorillonite.
Catalyst provided by the present invention can adopt ion-exchange, infusion process, coprecipitation, mechanical mixing or its combination to be prepared.When not containing binding agent and inorganic oxide matrix in described catalyst agent, the soluble salt solutions that described ion-exchange comprises with having absorption sulfur functional metal mixes with molecular sieve, ion-exchange is carried out at 70 ~ 90 DEG C, then filter, wash, dry except desolventizing, then make metal ion fixing over a molecular sieve through roasting.Described coprecipitation comprises and mixing having absorption sulfur functional metal oxide precursor (soluble-salt of such as metal) with molecular sieve, adds precipitating reagent and makes it formation hydroxide or carbonate deposition, then drying, roasting make precipitation be converted into oxide.Described precipitating reagent is selected from alkali compounds, preferred ammoniacal liquor, sodium carbonate or urea.Infusion process of the present invention comprises the soluble salt solutions impregnated zeolite described in use with absorption sulfur functional metal, then dry except desolventizing, then makes the soluble-salt of metal be converted into metal oxide through roasting.The temperature of described drying is 30 ~ 300 DEG C, preferably 35 ~ 200 DEG C; The temperature of roasting is 300 ~ 800 DEG C, preferably 400 ~ 700 DEG C, roasting time preferably 1 ~ 10 hour.
When described catalyst contains inorganic oxide matrix, al binder, can adopt molecular sieve, al binder, inorganic oxide matrix mixing, making beating, then dry method preparation, the wherein said metal with absorption sulfur functional is introduced in molecular sieve or in pulping process and is introduced in slurries before making beating, also can introduce after slurry dried.When having the metal of adsorption desulfurize function described in introducing after slurry dried, ion-exchange, infusion process, the precipitation method or mechanical mixing can be adopted to introduce.There is described in introducing dry, roasting after the metal of adsorption desulfurize function, can be undertaken by preceding method.
Catalyst of the present invention, in preparation process, described in have absorption sulfur functional metal oxide multiple method can be adopted to be incorporated in catalyst.Such as first can introduce a kind of metal oxide by coprecipitation, after drying, introduce other metal oxide by infusion process again; Or first in molecular sieve, introduce a kind of metal oxide by infusion process, then introduce other metal oxide respectively by coprecipitation; Or first in molecular sieve, introduce a kind of metal oxide by ion-exchange, then introduce other metal oxide respectively by infusion process.Can introduce a kind of metal oxide at every turn, also can introduce Multimetal oxide simultaneously, often kind of metal oxide can be introduced by one or many, such as, adopts the method for repeatedly flooding to introduce a kind of metal oxide.
Method for preparing catalyst provided by the invention, a kind of concrete embodiment comprises the steps: to be formed to comprise describedly mends the super-stable Y molecular sieves of gallium and the slurries of zinc oxide component through framework dealumination, drying, roasting.Wherein method that is dry and roasting can adopt existing method.Such as dry temperature can be 100 ~ 300 DEG C, and the time can be 1s ~ 100 hour, and the mode of drying can adopt oven dry, dries, spraying dry, pneumatic conveying drying.The temperature of roasting can be 500 ~ 750 DEG C, and roasting time can be 0.5 ~ 10 hour.Described zinc oxide component can be Zinc oxide powder and or zinc oxide precursor, when also comprising inorganic oxide matrix and/or al binder in described catalyst, described described the benefit in the super-stable Y molecular sieves of gallium and the slurries of zinc oxide component through framework dealumination that comprise also comprises described inorganic oxide matrix component and/or al binder component.Also comprise in described catalyst except described zinc oxide other when there is the metal oxide of absorption sulfur functional, comprise described in metal oxide that described other has an absorption sulfur functional can be incorporated into before drying described in framework dealumination mends the super-stable Y molecular sieves of gallium and the slurries of zinc oxide component then through super-dry, roasting, also can be incorporated in the particle after super-dry or roasting then through roasting or dry roasting by the mode of flooding.
Catalyst provided by the invention, a kind of preferred preparation method is as follows: by the described aqueous solution of mending the super-stable Y molecular sieves of gallium and the water soluble salt of zinc through framework dealumination, be beaten into slurries, wherein the concentration of the aqueous solution of the water soluble salt of zinc is 30 ~ 55 % by weight preferably 45 ~ 55 % by weight, described weight ratio of mending the aqueous solution of the super-stable Y molecular sieves of gallium and the water soluble salt of zinc through framework dealumination is 1:1 ~ 4, precipitating reagent is added under stirring, the consumption of precipitating reagent makes the pH value of the mixture obtained be 7.0 ~ 8.0, then at room temperature to 95 DEG C aging 1 ~ 5 hour preferably 2 ~ 4 hours, filter, washing, dry, alumina binder component and/or the making beating of inorganic oxide matrix component is introduced in roasting or slurries after weathering, then filter, washing, drying and roasting.Described precipitating reagent is the aqueous solution that ammoniacal liquor, carbonate solution or urea liquid are more preferably sodium carbonate or urea.The catalyst obtained has higher desulfurization degree.When precipitating reagent is ammoniacal liquor time, the concentration of ammoniacal liquor can be 5 ~ 17 % by weight, when for sodium carbonate or urea liquid, the concentration of aqueous sodium carbonate is 0.5 ~ 1.5mol/L, and the concentration of aqueous solution of urea is that to be preferably 0.2 ~ 2mol/L be such as 0.5 ~ 1.5mol/L to 0.05 ~ 2.5mol/L, after adding precipitating reagent, be preferable over aged at room temperature 2.5 ~ 3.5 hours, then filter, washing, makes the sodium oxide content in product be no more than 0.5 % by weight.Also comprise in described catalyst except zinc oxide other when there is the metal oxide of absorption sulfur functional, other described metal with absorption sulfur functional contain in the slurries of described gallium modification super-stable Y molecular sieves and zinc oxide component described in can be incorporated into, also can be introduced by the method for dipping after drying, roasting, and then through super-dry and roasting, the temperature of roasting can be 500 ~ 750 DEG C, and roasting time can be 0.5 ~ 10 hour.
Room temperature of the present invention is 15 ~ 40 DEG C.
According to sulfur method of the present invention, by the temperature preferably 200 ~ 500 DEG C of hydrocarbon ils and catalyst exposure, more preferably 300 ~ 500 DEG C are such as 300 ~ 400 DEG C, and the pressure of contact is 0.1 ~ 3.0MPa, and weight (hourly) space velocity (WHSV) is 2 ~ 25h
-1.The diluent gas of one or more in nitrogen, steam, hydrogen, carbon monoxide, carbon dioxide, hydrocarbon gas such as methane, ethane and fluid catalytic cracking (FCC) dry gas is preferably also introduced in described contact, volume fraction described in the atmosphere of contact shared by diluent gas is 10 ~ 40 volume %, be such as 15 ~ 35 volume %, it is such as 65 ~ 85 volume % that hydrocarbon ils accounts for 60 ~ 90 volume %.Introduce diluent gas and can reduce green coke, improve desulphurizing activated.
According to sulfur method of the present invention, before hydrocarbon ils and catalyst exposure, also by described catalyst reduction or hydrothermal aging can be carried out.Described by catalyst reduction, under being included in the temperature of 300 ~ 600 DEG C, catalyst is contacted with reducing gas, described reducing gas such as hydrogen or carbon monoxide.Catalyst agent is contacted 1 ~ 7 hour with water vapour under being included in 400 ~ 900 DEG C of temperature by described hydrothermal aging, and wherein in atmosphere, the ratio of steam is 70 ~ 100 volume %.
According to sulfur method of the present invention, described hydrocarbon ils and catalyst exposure can be carried out in fixed bed, fluid bed, moving bed, preferably carry out in fluid bed or moving bed.
According to sulfur method of the present invention, also comprise the step regenerated decaying catalyst, described regeneration comprises and being contacted with air at 450 ~ 800 DEG C by catalyst, makes the sulfur-containing compound in catalyst and carbon deposit oxidation.Catalyst after regeneration be used for desulfurization or through reduction or hydrothermal aging after for catalytic desulfurization.
Below by example, the present invention is described, but does not therefore limit the present invention.In embodiment, agents useful for same is commercial AR except indicating, and molecular sieve used is provided by Shandong catalyst branch company of China Petrochemical Industry.
Example 1
By 100g HY molecular sieve, (Shandong catalyst branch company produces, and butt, lattice constant is 2.455nm, and sial atomic molar ratio is 3.64, specific area 584m
2/ g) mix mutually with 1000mL ammonium acetate solution (concentration 1.5mol/L), and break into slurry, slurry (molecular sieve/ammonium acetate solution) is heated to 85 DEG C, then, adds by 10gGa (NO
3)
3and 5gNH
4the fluorine gallic acid aqueous ammonium 500mL that F is formulated, feed time 5 minutes, adds rear reaction 5h, and product after filtering, uses (NH
4)
2sO
4the aqueous solution (concentration 1.5mol/L) washs 2h at 80 DEG C, the weight ratio of molecular sieve and solution is 1:10, and then repeated washing once, namely ［ Ga ］ Y molecular sieve (lattice constant 2.445nm is obtained after drying, sial atomic molar ratio is 5.44, silicon gallium atomic molar ratio is 20, specific area 560m
2/ g).
Above-mentioned ［ Ga ］ Y molecular sieve 70 grams (butt) that obtain is joined 150 milliliters containing in the aqueous solution of zinc nitrate 58.3 grams, adding ammoniacal liquor to pH value under stirring is 7.5 ± 0.5, obtain colloid, left at room temperature is suction filtration after aging 3 hours, to spend gained filter cake after deionized water dry 4 hours of 150 ° of C, roasting 2 hours in 640 ° of C air again, then with 1000 milliliters of aqueous impregnation 4 hours containing 12.2 grams of cobalt nitrates, then roasting 2 hours in dry 4 hours, the 640 ° C air of 150 ° of C, obtains catalyst A.
Catalyst A consists of molecular sieve 70 % by weight, zinc oxide 25 % by weight, cobalt oxide 5 % by weight.
Example 2
By 100g USY molecular sieve, (Shandong catalyst branch company produces, and butt, lattice constant is 2.448nm, and sial atomic molar ratio is 4.77, specific area 570m
2/ g) mix mutually with 1000mL ammonium acetate solution (concentration 2.0mol/L), and break into uniform slurry, slurry (molecular sieve/ammonium acetate solution) is heated to 80 DEG C, then, adds lentamente by 15gGa (NO
3)
3and 15gNH
4the fluorine gallic acid ammonium salt solution 400mL that F is formulated, reaction 3h, product after filtering, uses NH
4cl solution (concentration 1.5mol/L) washs 2h(molecular sieve with solution than being 15:1 at 90 DEG C), and then repeat once, thoroughly wash away the fluoride in product, namely ［ Ga ］ Y (lattice constant 2.440nm is obtained after drying, sial atomic molar ratio is 6.98, silicon gallium atomic molar ratio is 10, specific area 560m
2/ g).
Above-mentioned ［ Ga ］ Y zeolite 70g(butt by obtaining) to mix with boehmite and kaolin and pull an oar, then spraying dry makes microballoon, and wherein alumina content is 20 % by weight, and kaolin content is 30 % by weight, and molecular sieve content is 50 % by weight.
Get 50 grams of above-mentioned microballoons and join 150 milliliters containing in the aqueous solution of zinc nitrate 58.3 grams, adding ammoniacal liquor to pH value under stirring is 7.5 ± 0.5, obtain colloid, left at room temperature is suction filtration after aging 3 hours, wash by 500ml deionized water, removing nitrate ion, by gained filter cake dry 4 hours of 150 ° of C, then roasting 2 hours in 640 ° of C air; Then with 300 milliliters of aqueous impregnation three times containing 61 grams of cobalt nitrates, each solution usage is 100 milliliters, dipping 4 hours, and roasting 2 hours in dry 4 hours, the 640 ° C air of 150 ° of C after each dipping, obtain catalyst B.
Catalyst B consists of molecular sieve 25 % by weight, aluminium oxide 10 % by weight, kaolin 15 % by weight, zinc oxide 25 % by weight, cobalt oxide 25 % by weight.
Example 3
By 100g NH
4(Shandong catalyst branch company produces Y molecular sieve, and butt, lattice constant is 2.465nm, and sial atomic molar ratio is 2.63, specific area 624m
2/ g) mix with 1000mL ammonium acetate solution (concentration 1.0mol/L), making beating, is heated to 75 DEG C by slurry (molecular sieve/acetic acid solution), then, slowly and equably adds by 2gGa (NO
3)
3and 2gNH
4the fluorine gallic acid aqueous ammonium 200mL that F is formulated, reaction 10h, product after filtering, uses (NH
4)
2sO
4the weight ratio that (concentration 1.5mol/L) washs 2h(ammonium sulfate and molecular sieve at 85 DEG C is 20:1), and then repeated washing once, thoroughly wash away the fluoride in product, namely ［ Ga ］ Y (lattice constant 2.460nm is obtained after drying, sial atomic molar ratio is 3.08, silicon gallium atomic molar ratio is 70, specific area 620m
2/ g).
70 grams above-mentioned [Ga] Y zeolite (butts) are joined 150 milliliters containing in the aqueous solution of zinc nitrate 69.8 grams, adding sodium carbonate liquor (concentration is 1mol/L) under stirring is 7.5 ± 0.5 to pH value, obtain colloid, left at room temperature is suction filtration after aging 3 hours, after spending deionized water, near sodium oxide content is lower than 0.5 % by weight, gained filter cake was 150 ° of C dryings 4 hours, in 640 ° of C air, roasting obtains catalyst C in 2 hours again, and it consists of molecular sieve 70 % by weight, zinc oxide 30 % by weight.
Example 4
40 grams of [Ga] Y zeolites (with example 2) are joined 250 milliliters containing in the aqueous solution of zinc nitrate 84 grams, adding ammoniacal liquor to pH value under stirring is 7.5 ± 0.5, obtain colloid, left at room temperature is suction filtration after aging 3 hours, spend the roasting 2 hours in dry 4 hours, the 640 ° C air of 150 ° of C of gained filter cake after deionized water, then with 100 milliliters of aqueous impregnation 4 hours containing 36.6 grams of nickel nitrates, in dry 4 hours, the 640 ° C air of 150 ° of C, roasting obtains catalyst D in 2 hours.
Catalyst D consists of molecular sieve 40 % by weight, zinc oxide 45 % by weight, nickel oxide 15 % by weight.
Example 5
By 100g USY molecular sieve, (Shandong catalyst branch company produces, and butt, lattice constant is 2.435nm, and sial atomic molar ratio is 9.48, specific area 495m
2/ g) mix with 1000mL ammonium acetate solution (2.0mol/L), and break into uniform slurry, be heated to 90 DEG C, then, slowly and equably add by 30gGa (NO
3)
3and 30gNH
4the fluorine gallic acid ammonium salt solution 1000mL that F is formulated, reaction 8h, product after filtering, uses (NH
4)
2sO
4(3.0mol/L) at 90 DEG C, wash 2h, and then repeat once, namely obtain ［ Ga ］ Y molecular sieve after drying, its lattice constant 2.430nm, sial atomic molar ratio is 14.3, and silicon gallium atomic molar ratio is 5, specific area 480m
2/ g.
Adopt above-mentioned ［ Ga ］ Y to press the method Kaolinite Preparation of Catalyst E of example 2, the addition unlike zinc nitrate in settling step is 81.6 grams, replaces cobalt nitrate solution in impregnation steps with 100 milliliters of solution containing 36.6 grams of nickel nitrates.
Catalyst E consists of molecular sieve 25 % by weight, aluminium oxide 10 % by weight, kaolin 15 % by weight, zinc oxide 35 % by weight, nickel oxide 15 % by weight.
Example 6
By 100g HY molecular sieve, (Shandong catalyst branch company produces, and butt, lattice constant is 2.455nm, and sial atomic molar ratio is 3.64, specific area 584m
2/ g) mix with 1000mL ammonium acetate solution (1.0mol/L), and break into uniform slurry, slurry is heated to 70 DEG C, then, slowly and equably adds by 5gGa (NO
3)
3and 5gNH
4the fluorine gallic acid ammonium salt solution 500mL that F is formulated, reaction 6h, product after filtering, uses (NH
4)
2sO
4(1.0mol/L) at 85 DEG C, wash 2h, and then repeated washing once, thoroughly wash away the fluoride in product, namely ［ Ga ］ Y molecular sieve (lattice constant 2.450nm is obtained after drying, sial atomic molar ratio is 4.39, and silicon gallium atomic molar ratio is 40, specific area 578m
2/ g).
By 70 grams of above-mentioned [Ga] Y molecular sieves (butt), 54 grams of Zinc oxide powders, mix with 70 grams of boehmites (by aluminium oxide) and pull an oar, spraying dry makes microballoon, then with 100 milliliters of aqueous impregnation 4 hours containing 12.7 grams of cobalt nitrates, in dry 4 hours, the 640 ° C air of 150 ° of C, roasting 2 hours, obtains catalyst F.
Catalyst F consists of molecular sieve 35 % by weight, zinc oxide 27 % by weight, cobalt oxide 3 % by weight, aluminium oxide 35 % by weight.
Example 7
By the method Kaolinite Preparation of Catalyst G of example 6, addition unlike molecular sieve is 40 grams, zinc oxide addition is 100 grams, and boehmite (by aluminium oxide) addition is 20 grams, replaces cobalt nitrate solution in impregnation steps with 100 milliliters of solution containing 84.6 grams of nickel nitrates.
Catalyst G consists of molecular sieve 20 % by weight, zinc oxide 50 % by weight, nickel oxide 20%, aluminium oxide 10%.
Example 8
By the method Kaolinite Preparation of Catalyst H of example 6, addition unlike molecular sieve is 60 grams, zinc oxide addition is 110 grams, and boehmite (by aluminium oxide) addition is 20 grams, replaces cobalt nitrate solution in impregnation steps with 100 milliliters of solution containing 15.1 grams of ferric nitrates.
Catalyst H consists of molecular sieve 30 % by weight, zinc oxide 55 % by weight, iron oxide 5%, aluminium oxide 10%.
Comparative example 1
By the method Kaolinite Preparation of Catalyst I of example 1, unlike [Ga] Y molecular sieve replaced with the HY molecular sieve of equivalent wherein, HY molecular sieve lattice constant used is 2.465nm(sial atomic molar ratio is 2.63, specific area 624m
2/ g).
Catalyst I consists of HY molecular sieve 70 % by weight, zinc oxide 25 % by weight, nickel oxide 5 % by weight.
Comparative example 2
By the method Kaolinite Preparation of Catalyst J of example 2, unlike the use of REY type molecular sieve, lattice constant is 2.468nm(sial atomic molar ratio is 2.41, specific area 607m
2/ g).
Catalyst J consists of REY type molecular sieve 25 % by weight, aluminium oxide 10 % by weight, kaolin 15 % by weight, zinc oxide 25 % by weight, cobalt oxide 25 % by weight.
Comparative example 3
By the method Kaolinite Preparation of Catalyst K of example 6, unlike the use of the REY type molecular sieve of P Modification, lattice constant is 2.468nm(sial atomic molar ratio is 2.41, specific area 607m
2/ g).
Catalyst K consists of molecular sieve 35 % by weight, zinc oxide 27 % by weight, cobalt oxide 3 % by weight, aluminium oxide 35 % by weight.
Embodiment 9
According to the method Kaolinite Preparation of Catalyst of embodiment 3, unlike, in catalyst preparation process, do not add sodium carbonate after [Ga] Y molecular sieve adds zinc nitrate solution, do not filter, do not wash, by [Ga] Y zeolite 70g(lattice constant 2.460nm obtained, sial atomic molar ratio is 3.08, and silicon gallium atomic molar ratio is 70, specific area 620m
2/ g) join 50 milliliters containing in the aqueous solution of zinc nitrate 69.8 grams, the sample of gained was 150 ° of C dryings 4 hours, then roasting obtains catalyst in 2 hours in 640 ° of C air.
Embodiment 10
According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike, the urea liquid with 10 % by weight replaces ammoniacal liquor adjust ph to be 7.5 ± 0.5, obtains colloid, finally obtains catalyst A 2.
Comparative example 4
Use REY type molecular sieve, lattice constant is 2.468nm(sial atomic molar ratio is 2.41, specific area 607m
2/ g).By this molecular sieve 70g(butt) to mix with boehmite and kaolin and pull an oar, then spraying dry makes microballoon, and wherein alumina content is 20 % by weight, and kaolin content is 30 % by weight, and molecular sieve content is 50 % by weight.
Get 50 grams of above-mentioned microballoons and join 150 milliliters containing in the aqueous solution of zinc nitrate 58.3 grams, adding sodium carbonate liquor (concentration 1M) to pH value under stirring is 7.5 ± 0.5, obtain colloid, left at room temperature is suction filtration after aging 3 hours, make sodium oxide content lower than 0.5 % by weight after spending deionized water, gained filter cake was 150 ° of C dryings 4 hours, then roasting obtains catalyst C in 2 hours in 640 ° of C air, and it consists of molecular sieve 70 % by weight, zinc oxide 30 % by weight.
Catalyst J2 consists of REY type molecular sieve 25 % by weight, aluminium oxide 10 % by weight, kaolin 15 % by weight, zinc oxide 25 % by weight, cobalt oxide 25 % by weight.
Example 11
The micro-anti-experimental provision of fixed bed is evaluated the desulfurization performance of embodiment of the present invention catalyst and comparative catalyst respectively.Loaded catalyst is 5g, reaction is carried out in nitrogen atmosphere, nitrogen flow is 30ml/min, feedstock oil employing sulphur concentration is the catalytically cracked gasoline of 635 μ g/g, wherein sulfur alcohol compound is 16 μ g/g, and thio-ether type compounds is 9.7 μ g/g, thiophane 27.3 μ g/g, thiophene and alkylthrophene 572.3 μ g/g(comprise thiophene, methylthiophene, ethylthiophene, thioxene etc.), benzothiophene 9.7 μ g/g.Reaction temperature 320 DEG C, feedstock oil weight space velocity 4 hours
-1, desulfurization degree and the yield of gasoline of 1 ~ 6 hour the results are shown in Table 1, and the octane number change before and after reaction is in table 2.Wherein, the computational methods of desulfurization degree and product yield are as follows:
The rear sulfur content of gasoline weight × reaction after desulfurization degree=100%-(reaction)/(gasoline feeding amount × feed sulphur content) × 100%
Gasoline weight/gasoline feeding amount × 100% after liquid product (gasoline) yield=absorption
As seen from the data in Table 1, catalyst desulfurizing rate of the present invention is high, and for desulfurization of hydrocarbon oil, liquid product yield is high.
Example 12
By the method for example 11, desulfurization performance evaluation is carried out to catalyst B, unlike first catalyst hydrogen reducing being used further to desulphurization reaction, reducing condition is 360 DEG C, 4 hours, hydrogen volume air speed 1000 time
-1.Desulfurization atmosphere is the gaseous mixture of 93 volume % nitrogen and 7 volume % hydrogen.
The desulfurization degree reacted first 5 minutes is 100%, and reacting desulfurization degree after 1 hour is 99.2%.After reaction carries out 6 hours, the desulfurization degree of catalyst still reaches 98%, and the yield of absorption 6 hours product liquids is 99.8%.Motor octane number adds 0.40 unit, and research octane number (RON) adds 0.38 unit, on average adds 0.39 unit.
Example 13
This example investigates the regenerability of catalyst.
By the catalyst A after inactivation, D 640 DEG C, be oxidized in air and regenerate for 2 hours, then carry out HDS evaluation by the method for example 11, the results are shown in Table 2.
From table 2, after catalyst regeneration of the present invention, performance can be recovered completely, and after repeatedly regenerating, still can keep desulphurizing ability and improve product octane number.
Table 1
Table 2
△ MON represents the value added of product MON
△ RON represents the value added of product RON
Table 3
The liquid product yield noted in * table 1 and table 3 is the catalytic desulfurization yield of 6 hours.
Claims (14)
1. a desulfurization of hydrocarbon oil catalyst, comprise the super-stable Y molecular sieves of gallium modification and there is the metal oxide of absorption sulfur functional, the super-stable Y molecular sieves of described gallium modification is the super-stable Y molecular sieves mending gallium through framework dealumination, the sial atomic molar ratio of the super stable molecular sieve of described gallium modification is 3.5 ~ 25, silicon gallium atomic molar ratio is 4 ~ 90, lattice constant is less than 2.46nm, the super-stable Y molecular sieves of described gallium modification is 15 ~ 98:2 ~ 85 with the weight ratio with metal oxide adsorb sulfur functional, and the described metal oxide adsorbing sulfur functional that has comprises zinc oxide.
2. according to catalyst according to claim 1, it is characterized in that, described catalyst comprises the super-stable Y molecular sieves of 20 ~ 75 % by weight gallium modifications, the zinc oxide of 22 ~ 60 % by weight, and other of 0 ~ 30 % by weight has the metal oxide adsorbing sulfur functional.
3. according to catalyst according to claim 2, it is characterized in that, described catalyst comprises the super-stable Y molecular sieves of 25 ~ 70 % by weight gallium modifications, the zinc oxide of 25 ~ 55 % by weight, and other of 0 ~ 20 % by weight has the metal oxide adsorbing sulfur functional.
4. according to catalyst according to claim 3, it is characterized in that, described catalyst comprises in the al binder of aluminium oxide 0 ~ 40 % by weight, with oxide basis 0 ~ 40 % by weight inorganic oxide matrix, and the super-stable Y molecular sieves of gallium modification and the described total content with the metal oxide of absorption sulfur functional are 50 ~ 100 % by weight.
5. according to catalyst according to claim 1, it is characterized in that, the sial atomic molar ratio of the super stable molecular sieve of described gallium modification is 5 ~ 25, and silicon gallium atomic molar ratio is 4 ~ 90, and surface area is 150 ~ 620m
2/ g.
6. according to catalyst according to claim 1, it is characterized in that, the preparation method of the described super-stable Y molecular sieves through framework dealumination benefit gallium is as follows: the ammonium acetate aqueous solution being 0.5 ~ 2.5mol/L by Y zeolite raw material and concentration mixes, then 70 ~ 90 DEG C are warming up to, add fluorine gallic acid ammonium salt solution, reaction 3 ~ 10h, product after filtering, wash away the fluoride in product, obtain the super-stable Y molecular sieves that framework dealumination mends gallium.
7. according to the catalyst described in any one of claim 2 ~ 4, it is characterized in that, other described metal oxide with absorption sulfur functional is one or more in the oxide of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt, and zinc oxide and other weight ratio with the metal oxide adsorbing sulfur functional are 1 ~ 20:1.
8. according to catalyst according to claim 4, it is characterized in that, described al binder is one or more in boehmite, Alumina gel; Described inorganic oxide matrix is one or more in aluminium oxide, silica, amorphous aluminum silicide, clay.
9. the preparation method of catalyst described in any one of claim 1 ~ 8, comprising: form the step comprising the slurries of described gallium modification super-stable Y molecular sieves and zinc oxide component, drying, roasting.
10. in accordance with the method for claim 9, it is characterized in that, the preparation method of described catalyst comprises the steps:
A) described gallium modification super-stable Y molecular sieves, zinc oxide component and water are pulled an oar form slurries; Contain in described slurries or do not contain al binder component, contain or do not contain inorganic oxide matrix component; Described zinc oxide component is Zinc oxide powder and/or zinc oxide precursor;
B) dry;
C) roasting.
11. in accordance with the method for claim 9, it is characterized in that, the preparation method of described catalyst comprises the steps:
A) described gallium modification super-stable Y molecular sieves, zinc oxide component and water are pulled an oar; Described zinc oxide component is zinc oxide precursor, and described zinc oxide precursor is the soluble-salt of zinc;
B) add precipitating reagent in the slurry dried obtained in step a), the consumption of precipitating reagent makes the pH value of the slurries obtained be 7 ~ 8, aging; Described precipitating reagent is one or more in ammoniacal liquor, carbonate solution, urea liquid;
C) slurries that step b) obtains directly are filtered, wash and introduce alumina binder component in the dry or slurries that obtain in step b) and/or then the making beating of inorganic oxide matrix component is filtered, to be washed and dry;
D) product roasting step c) obtained.
12. in accordance with the method for claim 11, it is characterized in that, the preparation method of described catalyst also comprises step e): other except zinc oxide of product step d) obtained has absorption sulfur functional aqueous metal solution dipping, dry, roasting.
13. 1 kinds of attached sulfur methods of hydrocarbon ils, comprise the step contacted at 200 ~ 500 DEG C with catalyst by gasoline, it is characterized in that, the catalyst that described catalyst provides for any one of claim 1 ~ 8.
14. in accordance with the method for claim 13, it is characterized in that, the temperature of described contact is 300 ~ 500 DEG C, and the pressure of contact is 0.1 ~ 3.0MPa, and weight space velocity is 2 ~ 25h
-1; Introduce nitrogen in contact, steam, hydrogen, carbon monoxide, carbon dioxide, boiling point are less than the hydrocarbon gas of 0 DEG C and one or more diluent gas in fluid catalytic cracking dry gas, diluent gas proportion described in the atmosphere of contact is 10 ~ 40 volume %.
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| CN106433741A (en) * | 2016-12-07 | 2017-02-22 | 郑州丽福爱生物技术有限公司 | Gasoline product desulfurizing agent, as well as preparation method and application thereof |
| CN106433749A (en) * | 2016-12-07 | 2017-02-22 | 郑州丽福爱生物技术有限公司 | Selective desulfurizing agent, preparation method thereof and application |
| CN106554803A (en) * | 2016-12-07 | 2017-04-05 | 郑州丽福爱生物技术有限公司 | A kind of gasoline desulfurizer and its preparation method and application |
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