CN104209142B - 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 refine hydrocarbon ils with solid, furtherly the present invention relates to the desulfurization of hydrocarbon ils.
Background technology
Sulphur in automobile-used oil product can cause serious atmosphere pollution, be that this various countries has formulated the strict standard automobile-used combustion of limitation
Sulfur content in material, the GB17930-2006 regulations that on December 6th, 1 implements, motor petrol（Ⅱ）Sulfur content be not more than
500ppm（Mass fraction）, motor petrol（Ⅲ）Sulfur content be not more than 150ppm（Mass fraction）.National environmental protection method in recent years
Advising has stricter limitation to the content of pollutant in product oil, and the ground such as Beijing and Shanghai takes the lead in state of enforcement IV discharge marks
Standard, more requires that sulfur content in gasoline is reduced to 50ppm（Mass fraction）Below.
At present, the method for removing sulphur in automobile-used oil product mainly has：Catalytic desulfurhydrogenation, catalytic cracking and desulfurizing, oxidation sweetening,
Solvent extraction desulfurization, biological desulphurization, absorption desulfurization, film desulfurization and photocatalysis desulfurization etc..Wherein absorption desulfurization is by by oil
The sulfur-containing compounds such as mercaptan, disulphide, thioether and thiophene-based in product are adsorbed on the sorbent, realize reducing sulfur content in oil products
Purpose, have the advantages that simple, easily and fast, be that current people compare one of desulfurization technology of concern.
USP5807475 discloses a kind of method that sulfur-containing compound is removed from hydrocarbon mixture, is included in 10~100
Hydrocarbon ils is contacted with adsorbent at DEG C, time of contact is enough to make the sulfur-containing compound in hydrocarbon ils be adsorbed onto on adsorbent；The suction
Attached dose is at least 150m selected from NiX, MoX, NiY zeolite and surface area2The montmorillonite of/g.
CN1714926 discloses a kind of molecular sieve and its preparation method for removing organic compounds containing sulfur in oil product.It is
It is loaded with the Y molecular sieve of copper or nickel, or the MCM-41 molecular sieves containing titanium.For the benzothiophene that is dissolved in normal octane
Removing, desulfurization degree is higher.
USP6150300 discloses a kind of preparation method of sulfur absorbent, including by the component of silicon oxide-containing, containing metal oxygen
The component of compound and the component containing zinc oxide mix, then the ball that the mixture is made 10~1000 microns of diameter.
The preparation method of sulfur absorbent disclosed in USP6184176, including zinc oxide, silica, aluminum oxide are mixed
Particle, dries, is impregnated with cobalt or compound containing cobalt after roasting, dries, is reduced the cobalt in adsorbent with reducing agent after roasting
Into zeroth order.The adsorbent is used for cracking gasoline or cracked diesel oil desulfurization, and adsorbing the temperature of desulfurization makes cracking gasoline or diesel oil be gas
State, preferably gasoline absorbing desulfurization temperature are 204~427 DEG C（400~800 °F）, the temperature of diesel oil adsorption desulfurizing is 260~487
℃（500~900 °F）, desulfurizing agent after absorption is through regenerating and activation Posterior circle is used.CN 1130253C contain there is provided one kind
The novel absorbent composition of zinc oxide, silica, aluminum oxide and nickel or cobalt, and the preparation method of this adsorbent is provided.
The method prepare first containing zinc oxide, silica, aluminum oxide carrier, then by impregnate introduce nickel.The adsorbent can use
In removing sulphur from cracking gasoline or diesel fuel.
Zinc oxide, expanded perlite and aluminum oxide are included using promoter metals such as cobalt and nickel dipping in CN 1208124C
Adsorbing agent carrier, then reduction accelerator at appropriate temperatures, prepares the adsorbent for removing sulfide in cracking gasoline.
While above-mentioned adsorbent removes sulfur in gasoline under hydro condition, inevitably due to alkene saturation cause it is pungent
The reduction of alkane value.
CN 101433821A provide a kind of adsorbent for reducing sulfur content in hydrocarbon oils, including rare earth faujasite, active metal
Oxide and carrier, wherein carrier include aluminum oxide and zinc oxide；By above-mentioned rare earth faujasite and carrier mixture in advance into
Shape is porous heat-resistant solid particle, then introduces metal active constituent on this solid particle, prepares the adsorbent.
CN 101434854A provide a kind of adsorbent for reducing sulfur content of light hydrocarbon oil, including the boiling of P Modification rare earth octahedral
Stone, reactive metal oxides and carrier, wherein carrier include aluminum oxide and zinc oxide；By above-mentioned rare earth faujasite through P Modification
Porous heat-resistant solid particle is pre-formed into carrier mixture afterwards, then metal active constituent is introduced on this solid particle, made
It is standby to obtain the adsorbent.
Although above-mentioned two pieces patent can improve the octane number of gasoline, can only within the shorter reaction time have compared with
Good desulfurization and raising octane number effect, desulfurization time example desulfurization degree more long decline, and octane number increase rate is limited, liquid yield
It is not high.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst of desulfurization under high temperature for gasoline, and the catalyst contains
There is the modified Y type molecular sieve of gallium, it is possible to increase the octane number of gasoline.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, containing the modified faujasite molecular sieve of gallium and with absorption sulphur work(
The metal oxide of energy, the sial atomic molar ratio of the molecular sieve is 3.5~50, and silicon gallium atomic molar ratio is 4~90, structure cell
Constant is less than 24.6nm, and molecular sieve is with the weight ratio of the metal oxide with absorption sulfur functional（15~98）:（2~85）,
The modified faujasite of the gallium is the super-stable Y molecular sieves that gallium is mended through framework dealumination, and gallium takes in the skeleton structure of the molecular sieve
For the part aluminium in former skeleton structure, the metal oxide of the absorption sulfur functional includes zinc oxide.
The present invention provides a kind of sulfur method, including the step of gasoline is contacted with above-mentioned catalyst, wherein the temperature for contacting
It is 200~500 DEG C to spend, and the pressure of contact is 0.1~1.0MPa, and nitrogen, vapor, hydrogen, carbon monoxide, two are introduced in contact
Carbonoxide, boiling point less than one or more in 0 DEG C of hydrocarbon gas and fluid catalytic cracking dry gas, in atmosphere shared by the gas
Ratio is 10~40 volume %
The desulphurization catalyst that the present invention is provided, for gasoline desulfurization, can improve gasoline within the operating time more long
Octane number simultaneously maintains desulfurization of hydrocarbon oil rate higher, and yield of gasoline is high；The catalyst stability is good, through repeatedly regeneration, can maintain
High desulfurization activity and raising octane number ability.Inventive desulfurization method, hydrocarbon ils high income, desulfuration efficiency is high, gasoline octane
Value is improved.The sulfur method that the present invention is provided, catalyst not only can be with the sulphur in adsorbed gasoline, can also be in the acid of molecular sieve
Under heart effect, the sulphur of absorption is converted into hydrogen sulfide, desulfurization performance high is kept such that it is able to the long period, can deposited in no hydrogen
Desulfurization under the conditions.
Specific embodiment
According to catalyst of the present invention, the modified faujasite molecular sieve of described gallium is to mend gallium by framework dealumination
Super-stable Y molecular sieves, the sial atomic molar ratio preferably 5~25 of molecular sieve, silicon gallium atomic molar ratio be 4~90, it is described
The specific surface area of molecular sieve is 150~620m2/ g, lattice constant is less than 2.46nm, for example, 2.43~2.47nm.
The super-stable Y molecular sieves that gallium is mended through framework dealumination of the present invention, the present invention is referred to as ［ Ga ］ Y molecular sieve, and gallium is located at
In the skeleton structure of molecular sieve, the part aluminium in Y type molecular sieve original skeleton structure is instead of.It is described to mend the super of gallium through framework dealumination
Stabilization Y-type molecular sieve is the Y type molecular sieve with skeleton gallium atom of secondary synthesis, can be prepared according to existing method, for example, press
Prepared according to method disclosed in USP5238675.The super-stable Y molecular sieves that gallium is mended through framework dealumination, preferred preparation method is such as
Under：Y type molecular sieve raw material is mixed with ammonium acetate solution, and breaks into slurry, by slurry be heated to 50~95 DEG C preferably 70 DEG C~
90 DEG C, then, slowly it is homogeneously added into by Ga (NO3)3And NH4The fluorine gallic acid ammonium salt solution that F is formulated, reacts 3~10h, produces
Thing after filtering, with (NH4)2SO4Or NH4Cl solution wash, such as at 65~95 DEG C preferably at 80~90 DEG C washing 2~
4h, the washing may be repeated one or more times, and to wash away the fluoride in product, gallium modified Y types point be obtained final product after dry, roasting
Son sieve.Described Y type molecular sieve raw material is Si-Al molecular sieve, and with sial skeleton structure, described Y type molecular sieve raw material can be with
It is NH4One or more in Y, HY, USY, REY, REHY, REUSY, the concentration of the ammonium acetate solution can for 0.5~
2.5mol/L, wherein ammonium acetate solution can be 5~20 with the weight ratio of Y type molecular sieve raw material:1 preferably 8~15:1, it is described
Slowly it is homogeneously added into for example：Feed rate is 50~500mL fluorine gallic acids ammonium salt solution/gram Y type molecular sieve raw material/hour.Institute
Stating fluorine gallic acid ammonium salt solution can be by by Ga (NO3)3、NH4F and the method for water mixing are prepared, wherein Ga (NO3)3With NH4The weight of F
Amount is than being 2~1:1, Ga (NO in solution3)3With NH4The total content of F is 1~10 weight %, fluorine gallic acid ammonium salt solution and Y type molecular sieve
The weight ratio of raw material is 1~15:1, preferably 2~12:1.The ammonium chloride or ammonium sulfate concentration of the washing can be 0.5
~3mol/L, ammonium sulfate can be 5~20 with the weight ratio of molecular sieve:1.
According to catalyst of the present invention, the metal oxide with absorption sulfur functional be selected from I A races, II A races,
One or more in III A races or transition metal oxide, preferably Na, K, Mg, Ca, Al, lanthanide series metal, Sc, Ti, V, Cr,
One or more in the oxide of Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt.It is described with suction
The ratio between the metal oxide of attached sulfur functional and molecular sieve are（15~98）:（2~85）.
According to catalyst of the present invention, described catalyst includes the superstable gamma-type molecule that 20~75 weight % galliums are modified
Other of sieve, the zinc oxide of 22~60 weight %, 0~30 weight % such as 1~25 weight % have the metal oxidation of absorption sulfur functional
Thing；It is further preferred that described catalyst includes the super-stable Y molecular sieves that 25~70 weight % galliums are modified, the oxidation of 25~55 weight %
Zinc, other of 0~20 weight % such as 2~15 weight % have the metal oxide for adsorbing sulfur functional.It is described other have absorption
The metal oxide of sulfur functional be Na, K, Mg, Ca, Al, lanthanide series metal, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W,
One or more in the oxide of Ru, Rh, Pd, Ag, Cd, Au and Pt, preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo,
One or more in the oxide of W, Ru, Rh, Pd, Ag, Cd, Au and Pt.Other described have the gold of absorption sulfur functional
Category oxide is preferably one or more in cobalt oxide, nickel oxide, cupric oxide, molybdenum oxide, aluminum oxide, iron oxide, zinc oxide
Weight ratio with other metal oxides with absorption sulfur functional is 1~20:1, for example, 1~15:1, preferably 1~
5:1.The metal oxide is derived from the oxide or oxide precursor of metal, and the oxide precursor is preferably the solvable of metal
Property salt, the nitrate of such as metal, sulfate, chloride, carbonate or acylate, described organic salt such as acetate,
Formates.Described zinc oxide its average grain diameter（Diameter）Preferably smaller than 100nm, for example, 10~75nm.
According to catalyst of the present invention, can also contain one or more in al binder, inorganic oxide matrix, with
On the basis of total catalyst weight, molecular sieve and the content with absorption sulfur functional metal oxide are 50~100 weight %, preferably
60~99.6 weight %, for example, 50~90 weight %, the content of al binder is no more than 40 weight %, for example, 5 in terms of aluminum oxide
~35 weight %, the content of inorganic matter matrix of oxide is no more than 40 weight, preferably 0~30 weight % in terms of oxide.This hair
The desulphurization catalyst of bright offer may include the superstable gamma-type molecule that gallium is mended by framework dealumination of 30 weight %~70 weight %
Sieve, the zinc oxide of 25~55 weight %, 3~25 weight % selected from VIII group 4 transition metal in a kind of VIII family metal oxide, 0
The inorganic matter matrix of~35 weight the % such as binding agent of 3~25 weight % and 0~20 weight % such as 1~15 weight %.It is described
Al binder is boehmite and/or Alumina gel.The inorganic oxide matrix is selected from aluminum oxide, silica, amorphous silicon
One or more in aluminium, clay.The clay is selected from bentonite, galapectite, kaolinite, montmorillonite, mica or palygorskite, day
Right and artificial synthesized mica-montmorillonite, such as rectorite, Yun Mengshi, mica-montmorillonite, illite-montmorillonite, glauconite-illiteracy
De- stone, chlorite-montmorillonite, mica-vermiculite or kaolinite-montmorillonite.
Catalyst provided by the present invention can use ion-exchange, infusion process, coprecipitation, mechanical mixing or its group
Conjunction is prepared.When binding agent and inorganic oxide matrix is free of in the catalyst agent, the ion-exchange includes
Mixed with molecular sieve with the soluble salt solutions with absorption sulfur functional metal, ion exchange is carried out at 70~90 DEG C, then
Filtering, washing, dry removing solvent, then metal ion is fixed over a molecular sieve by roasting.The coprecipitation includes will
With absorption sulfur functional metal oxide precursor（The soluble-salt of such as metal）Mix with molecular sieve, add precipitating reagent to be allowed to shape
Hydrate or carbonate deposition, then precipitation is converted into oxide through drying, roasting.Described precipitating reagent is selected from alkalization
Compound, preferably ammoniacal liquor, sodium carbonate or urea.Infusion process of the present invention include with it is described there is absorption sulfur functional metal can
Dissolubility salt solution impregnation molecular sieve, then dries and removes solvent, then the soluble-salt of metal is converted into metal oxygen by roasting
Compound.The dry temperature is 30~300 DEG C, preferably 35~200 DEG C；The temperature of roasting be 300~800 DEG C, preferably 400~
700 DEG C, roasting time preferably 1~10 hour.
When the catalyst contains inorganic oxide matrix, al binder, can use molecular sieve, al binder, nothing
Machine matrix of oxide mixes, mashing, and then prepared by dry method, wherein the metal with absorption sulfur functional is before mashing
In being introduced into molecular sieve or being introduced into slurries in pulping process, it is also possible to introduced after slurries drying.After being dried in slurries
When there is the metal of absorption desulfurizing function described in introducing, can be drawn using ion-exchange, infusion process, the precipitation method or mechanical mixing
Enter.Dry, roasting after the metal with absorption desulfurizing function is introduced, can be carried out by preceding method.
Catalyst of the present invention, in preparation process, the metal oxide with absorption sulfur functional can be used
Various methods are incorporated into catalyst.For example a kind of metal oxide first can be introduced with coprecipitation, again with dipping after drying
Method introduces other metal oxides；Or first introduce a kind of metal oxide in molecular sieve with infusion process, then with co-precipitation
Method introduces other metal oxides respectively；Or a kind of metal oxide is first introduced in molecular sieve with ion-exchange, then
Introduce other metal oxides respectively with infusion process.A kind of metal oxide can every time be introduced, it is also possible to while introducing various
Metal oxide, every kind of metal oxide can be introduced with one or many, for example, introducing a kind of gold using the method for multiple dipping
Category oxide.
A kind of method for preparing catalyst that the present invention is provided, specific embodiment comprises the following steps：Formation includes institute
The slurries of super-stable Y molecular sieves with zinc oxide component that gallium is mended through framework dealumination are stated, is dried, roasting.Wherein dry and be calcined
Method can use existing method.Such as dry temperature can be 100~300 DEG C, and the time can be 1s~100 hour, dry
Mode can using drying, dry, being spray-dried, pneumatic conveying drying.The temperature of roasting can be 500~750 DEG C, and roasting time can
Think 0.5~10 hour.Described zinc oxide component can be Zinc oxide powder and/or zinc oxide precursor, when described catalyst
In when also including inorganic oxide matrix and/or al binder, it is described including the superstable gamma-type point that gallium is mended through framework dealumination
Also include the inorganic oxide matrix component and/or al binder component in son sieve and the slurries of zinc oxide component.When described
Catalyst in also include in addition to the zinc oxide other have absorption sulfur functional metal oxide when, other described
Metal oxide with absorption sulfur functional can be previously introduced described including the surpassing through framework dealumination benefit gallium in drying
In the slurries of stabilization Y-type molecular sieve and zinc oxide component and then by drying, roasting, it is also possible to be incorporated into by way of dipping through
In the particle crossed after drying or being calcined and then by roasting or dry roasting.
A kind of catalyst that the present invention is provided, preferred preparation method is as follows：Described is mended into the super of gallium through framework dealumination
Stabilization Y-type molecular sieve mixes with the aqueous solution of the water soluble salt of zinc, is beaten into slurries, the wherein aqueous solution of the water soluble salt of zinc
Concentration be 30~55 weight % preferably 45~55 weight %, described super-stable Y molecular sieves and zinc that gallium is mended through framework dealumination
The weight ratio of the aqueous solution of water soluble salt is 1:1~4, the lower addition precipitating reagent of stirring, the consumption of precipitating reagent makes the mixing for obtaining
The pH value of thing is 7.0~8.0, then in room temperature to preferably 2~4 hours aging 1~5 hour at 95 DEG C, filter, wash, drying,
Alumina binder component and/or the mashing of inorganic oxide matrix component are introduced in roasting or slurries after weathering, then
Filtering, washing, dry and roasting.Described precipitating reagent for ammoniacal liquor, carbonate solution or urea liquid be more preferably sodium carbonate or
The aqueous solution of urea.Resulting catalyst has desulfurization degree higher.When precipitating reagent is ammoniacal liquor, the concentration of ammoniacal liquor can
Think 5~17 weight %, when for sodium carbonate or urea liquid, the concentration of aqueous sodium carbonate is 0.5~1.5mol/L, urea
The concentration of the aqueous solution is, for example, 0.5~1.5mol/L for 0.05~2.5mol/L is preferably 0.2~2mol/L, adds precipitating reagent
Afterwards, preferably at room temperature aging 2.5~3.5 hours, then filter, wash, the sodium oxide content in product is no more than 0.5 weight
Amount %.When also there is the metal oxide of absorption sulfur functional including other in addition to zinc oxide in described catalyst,
It is described containing the gallium modified super-stable Y molecular sieves and zinc oxide that there is other described the metal of absorption sulfur functional can be incorporated into
Method in the slurries of component, or by impregnating after drying, roasting is introduced, then drying and roasting, roasting
The temperature of burning 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, preferably 200~500 DEG C of the temperature that hydrocarbon ils is contacted with catalyst is more excellent
It is, for example, 300~400 DEG C to select 300~500 DEG C, and the pressure of contact is 0.1~3.0MPa, and weight (hourly) space velocity (WHSV) is 2~25h-1.It is described to connect
Nitrogen, vapor, hydrogen, carbon monoxide, carbon dioxide, hydrocarbon gas such as methane, ethane and stream are preferably also introduced in touching
Fluidized catalytic cracking（FCC）The diluent gas of one or more in dry gas, the body described in the atmosphere of contact shared by diluent gas
Integration rate is 10~40 volume %, for example, 15~35 volume %, and it is, for example, 65~85 volume % that hydrocarbon ils accounts for 60~90 volume %.Introduce
Diluent gas can reduce green coke, improve desulphurizing activated.
According to sulfur method of the present invention, before hydrocarbon ils is contacted with catalyst, can also by the catalyst reduction or
Carry out hydrothermal aging.It is described that catalyst reduction is included at a temperature of 300~600 DEG C, catalyst is connect with reducing gas
Touch, the reducing gas such as hydrogen or carbon monoxide.The hydrothermal aging is included at a temperature of 400~900 DEG C, by catalyst
Agent is contacted 1~7 hour with water vapour, and the ratio of vapor is 70~100 volume % wherein in atmosphere.
According to sulfur method of the present invention, described hydrocarbon ils is contacted with catalyst can be in fixed bed, fluid bed, shifting
Carried out in dynamic bed, preferably carried out in fluid bed or moving bed.
According to sulfur method of the present invention, also including being regenerated to decaying catalyst the step of, the regeneration bag
Include by catalyst at 450~800 DEG C with air contact, aoxidize sulfur-containing compound in catalyst and carbon deposit.After regeneration
Catalyst is used for desulfurization or is used for catalytic desulfurization after reduction or hydrothermal aging.
The present invention is illustrated below by example, but and is not so limited the present invention.Agents useful for same is in addition to indicating in embodiment
It is AR purchased in market, molecular sieve used is provided by sinopec Shandong catalyst branch company.
Example 1
By 100g HY molecular sieves, (Shandong catalyst branch company produces, and butt, lattice constant is 2.455nm, sial atom
Mol ratio is 3.64, specific surface area 584m2/ g) mutually mixed with 1000mL ammonium acetate solutions (concentration 1.5mol/L), and slurry is broken into,
Slurry (molecular sieve/ammonium acetate solution) is heated to 85 DEG C, then, is added by 10gGa (NO3)3And 5gNH4The fluorine that F is formulated
Gallic acid aqueous ammonium 500mL, feed time 5 minutes reacts 5h after adding, product after filtering, with (NH4)2SO4The aqueous solution is (dense
Degree 1.5mol/L) 2h is washed at 80 DEG C, molecular sieve is 1 with the weight ratio of solution:10, then repeat and washed once, dry
After obtain final product ［ Ga ］ Y molecular sieve (lattice constant 2.445nm, sial atomic molar ratio be 5.44, silicon gallium atomic molar ratio be 20, than
Surface area 560m2/g）.
Above-mentioned 70 grams of ［ Ga ］ Y molecular sieve that will be obtained（Butt）It is added to 150 milliliters of aqueous solution containing 58.3 grams of zinc nitrate
In, the lower addition ammoniacal liquor of stirring is 7.5 ± 0.5 to pH value, obtains colloid, and suction filtration after aging 3 hours is stood at room temperature, uses deionization
By gained filter cake in 150 °C of dryings 4 hours after water washing, it is calcined 2 hours in 640 °C of air, is then contained with 1000 milliliters
12.2 grams of aqueous impregnations of cobalt nitrate 4 hours, are then calcined 2 hours in 150 °C of dryings 4 hours, 640 °C of air, obtain
Catalyst A.
Catalyst A compositions are the weight % of molecular sieve 70, the weight % of zinc oxide 25, the weight % of cobalt oxide 5.
Example 2
By 100g USY molecular sieves, (Shandong catalyst branch company produces, and butt, lattice constant is 2.448nm, sial atom
Mol ratio is 4.77, specific surface area 570m2/ g) mutually mixed with 1000mL ammonium acetate solutions (concentration 2.0mol/L), and break into uniform
Slurry, slurry (molecular sieve/ammonium acetate solution) is heated to 80 DEG C, then, be slowly added into by 15gGa (NO3)3With
15gNH4The fluorine gallic acid ammonium salt solution 400mL that F is formulated, reacts 3h, and product after filtering, uses NH4Cl solution (concentration 1.5mol/
L) 2h is washed at 90 DEG C（Molecular sieve is 15 with solution ratio：1）, then repeat once, the fluoride in product is thoroughly washed away,
［ Ga ］ Y is obtained final product after drying, and (lattice constant 2.440nm, sial atomic molar ratio is 6.98, and silicon gallium atomic molar ratio is 10, compares table
Area 560m2/g）.
Above-mentioned ［ Ga ］ the Y type molecular sieve 70g that will be obtained（Butt）Mix mashing with boehmite and kaolin, then spray
Mist is dried and is made microballoon, and wherein alumina content is 20 weight %, and kaolin content is 30 weight %, and molecular sieve content is 50 weights
Amount %.
Take 50 grams of above-mentioned microballoons to be added in 150 milliliters of aqueous solution containing 58.3 grams of zinc nitrate, stirring is lower to add ammoniacal liquor extremely
PH value is 7.5 ± 0.5, obtains colloid, and suction filtration after aging 3 hours is stood at room temperature, is washed with 500ml deionized waters, removes nitre
Acid ion, by gained filter cake in 150 °C of dryings 4 hours, is then calcined 2 hours in 640 °C of air；Then with 300 milliliters
Containing 61 grams of aqueous impregnations of cobalt nitrate three times, each solution usage is 100 milliliters, dipping 4 hours, and every time dipping after
It is calcined 2 hours in 150 °C of dryings 4 hours, 640 °C of air, obtains catalyst B.
Catalyst B composition for the weight % of molecular sieve 25, the weight % of aluminum oxide 10, the weight % of kaolin 15, the weight % of zinc oxide 25,
The weight % of cobalt oxide 25.
Example 3
By 100g NH4(Shandong catalyst branch company produces Y molecular sieve, butt, and lattice constant is 2.465nm, and sial is former
Sub- mol ratio is 2.63, specific surface area 624m2/ g) mixed with 1000mL ammonium acetate solutions (concentration 1.0mol/L), mashing will be starched
Material (molecular sieve/acetic acid solution) is heated to 75 DEG C, then, is slowly homogeneously added into by 2gGa (NO3)3And 2gNH4F prepare and
Into fluorine gallic acid aqueous ammonium 200mL, react 10h, product after filtering, with (NH4)2SO4(concentration 1.5mol/L) is at 85 DEG C
Washing 2h（Ammonium sulfate is 20 with the weight ratio of molecular sieve:1）, then repeat and washed once, in thoroughly washing away product
Fluoride, ［ Ga ］ Y is obtained final product after drying, and (lattice constant 2.460nm, sial atomic molar ratio is 3.08, and silicon gallium atomic molar ratio is
70, specific surface area 620m2/g）.
By 70 grams of above-mentioned [Ga] Y type molecular sieves（Butt）It is added in 150 milliliters of aqueous solution containing 69.8 grams of zinc nitrate, stirs
Mix lower addition sodium carbonate liquor（Concentration is 1mol/L）It is 7.5 ± 0.5 to pH value, obtains colloid, aging 3 hours is stood at room temperature
Suction filtration afterwards, is washed with deionized rear near sodium oxide content less than 0.5 weight %, gained filter cake in 150 °C of dryings 4 hours, then
Roasting obtains catalyst C in 2 hours in 640 °C of air, consisting of the weight % of molecular sieve 70, the weight % of zinc oxide 30.
Example 4
By 40 grams of [Ga] Y type molecular sieves（With example 2）It is added in 250 milliliters of aqueous solution containing 84 grams of zinc nitrate, stirring
Lower addition ammoniacal liquor to pH value is 7.5 ± 0.5, obtains colloid, and suction filtration after aging 3 hours is stood at room temperature, is washed with deionized
Gained filter cake is calcined 2 hours in 150 °C of dryings 4 hours, 640 °C of air afterwards, then with 100 milliliters containing 36.6 grams of nickel nitrates
Aqueous impregnation 4 hours, roasting obtains catalyst D in 2 hours in 150 °C of dryings 4 hours, 640 °C of air.
Catalyst D compositions are the weight % of molecular sieve 40, the weight % of zinc oxide 45, the weight % of nickel oxide 15.
Example 5
By 100g USY molecular sieves, (Shandong catalyst branch company produces, and butt, lattice constant is 2.435nm, sial atom
Mol ratio is 9.48, specific surface area 495m2/ g) mix with 1000mL ammonium acetate solutions (2.0mol/L), and break into uniform slurry
Material, is heated to 90 DEG C, then, is slowly homogeneously added into by 30gGa (NO3)3And 30gNH4The fluorine gallic acid ammonium that F is formulated is molten
Liquid 1000mL, react 8h, product after filtering, with (NH4)2SO4(3.0mol/L) washs 2h at 90 DEG C, then repeats one
It is secondary, ［ Ga ］ Y molecular sieve, its lattice constant 2.430nm are obtained final product after drying, sial atomic molar ratio is 14.3, silicon gallium atomic molar
Than being 5, specific surface area 480m2/g。
Catalyst E is prepared by the method for example 2 using above-mentioned ［ Ga ］ Y, unlike in settling step zinc nitrate addition
It is 81.6 grams to measure, and cobalt nitrate solution is replaced with 100 milliliters of solution containing 36.6 grams of nickel nitrates in impregnation steps.
Catalyst E composition for the weight % of molecular sieve 25, the weight % of aluminum oxide 10, the weight % of kaolin 15, the weight % of zinc oxide 35,
The weight % of nickel oxide 15.
Example 6
By 100g HY molecular sieves, (Shandong catalyst branch company produces, and butt, lattice constant is 2.455nm, sial atom
Mol ratio is 3.64, specific surface area 584m2/ g) mix with 1000mL ammonium acetate solutions (1.0mol/L), and break into uniform slurry
Material, 70 DEG C are heated to by slurry, then, are slowly homogeneously added into by 5gGa (NO3)3And 5gNH4The fluorine gallic acid that F is formulated
Ammonium salt solution 500mL, react 6h, product after filtering, with (NH4)2SO4(1.0mol/L) washs 2h at 85 DEG C, then repeats
Washed once, thoroughly wash away the fluoride in product, ［ Ga ］ Y molecular sieve is obtained final product after drying, and (lattice constant 2.450nm, sial is former
Sub- mol ratio is 4.39, and silicon gallium atomic molar ratio is 40, specific surface area 578m2/g）.
By 70 grams of above-mentioned [Ga] Y molecular sieves（Butt）, 54 grams of Zinc oxide powders, with 70 grams of boehmites（By aluminum oxide
Meter）Mixing mashing, spray drying is made microballoon, then with 100 milliliters of aqueous impregnations for containing 12.7 grams of cobalt nitrates 4 hours, in
It is calcined 2 hours in 150 °C of dryings 4 hours, 640 °C of air, obtains catalyst F.
Catalyst F compositions are the weight % of molecular sieve 35, the weight % of zinc oxide 27, the weight % of cobalt oxide 3, the weight % of aluminum oxide 35.
Example 7
Catalyst G is prepared by the method for example 6, the difference is that the addition of molecular sieve is 40 grams, zinc oxide addition is
100 grams, boehmite（Based on aluminum oxide）Addition is 20 grams, and 84.6 grams of nickel nitrates are contained with 100 milliliters in impregnation steps
Solution replaces cobalt nitrate solution.
Catalyst G compositions are the weight % of molecular sieve 20, the weight % of zinc oxide 50, nickel oxide 20%, aluminum oxide 10%.
Example 8
Catalyst H is prepared by the method for example 6, the difference is that the addition of molecular sieve is 60 grams, zinc oxide addition is
110 grams, boehmite（Based on aluminum oxide）Addition is 20 grams, and 15.1 grams of ferric nitrates are contained with 100 milliliters in impregnation steps
Solution replaces cobalt nitrate solution.
Catalyst H compositions are the weight % of molecular sieve 30, the weight % of zinc oxide 55, iron oxide 5%, aluminum oxide 10%.
Comparative example 1
Catalyst I is prepared by the method for example 1, the difference is that replacing [Ga] Y molecules therein with the HY molecular sieves of equivalent
Sieve, HY molecular sieves lattice constant used is 2.465nm（Sial atomic molar ratio is 2.63, specific surface area 624m2/g）.
Catalyst I compositions are the weight % of HY molecular sieves 70, the weight % of zinc oxide 25, the weight % of nickel oxide 5.
Comparative example 2
Catalyst J is prepared by the method for example 2, the difference is that using REY type molecular sieves, lattice constant is 2.468nm（Silicon
Aluminium atom mol ratio is 2.41, specific surface area 607m2/g）.
Catalyst J compositions are the weight % of REY types molecular sieve 25, the weight % of aluminum oxide 10, the weight % of kaolin 15, zinc oxide 25
Weight %, the weight % of cobalt oxide 25.
Comparative example 3
Catalyst K is prepared by the method for example 6, the difference is that using the REY type molecular sieves of P Modification, lattice constant is
2.468nm（Sial atomic molar ratio is 2.41, specific surface area 607m2/g）.
Catalyst K compositions are the weight % of molecular sieve 35, the weight % of zinc oxide 27, the weight % of cobalt oxide 3, the weight % of aluminum oxide 35.
Embodiment 9
Method according to embodiment 3 prepares catalyst, unlike, in catalyst preparation process, [Ga] Y molecular sieve adds
Enter and do not add sodium carbonate after zinc nitrate solution, do not filter, do not wash, [Ga] the Y type molecular sieve 70g that will be obtained（Lattice constant
2.460nm, sial atomic molar ratio is 3.08, and silicon gallium atomic molar ratio is 70, specific surface area 620m2/g）It is added to 50 milliliters
In the aqueous solution containing 69.8 grams of zinc nitrate, the sample of gained is calcined 2 hours in 150 °C of dryings 4 hours in 640 °C of air
Obtain catalyst.
Embodiment 10
Method according to embodiment 1 prepares catalyst, unlike, replace ammoniacal liquor to adjust with the urea liquid of 10 weight %
PH value is 7.5 ± 0.5, obtains colloid, finally gives catalyst A2.
Comparative example 4
Using REY type molecular sieves, lattice constant is 2.468nm（Sial atomic molar ratio is 2.41, specific surface area 607m2/
g）.By molecular sieve 70g（Butt）Mix mashing with boehmite and kaolin, then spray drying is made microballoon, wherein
Alumina content is 20 weight %, and kaolin content is 30 weight %, and molecular sieve content is 50 weight %.
Take 50 grams of above-mentioned microballoons to be added in 150 milliliters of aqueous solution containing 58.3 grams of zinc nitrate, stirring is lower to add sodium carbonate
Solution（Concentration 1M）It is 7.5 ± 0.5 to pH value, obtains colloid, suction filtration after aging 3 hours is stood at room temperature, is washed with deionized water
Make sodium oxide content after washing less than 0.5 weight %, gained filter cake is calcined 2 small in 150 °C of dryings 4 hours in 640 °C of air
When obtain catalyst C, consisting of the weight % of molecular sieve 70, the weight % of zinc oxide 30.
Catalyst J2 compositions are the weight % of REY types molecular sieve 25, the weight % of aluminum oxide 10, the weight % of kaolin 15, zinc oxide 25
Weight %, the weight % of cobalt oxide 25.
Example 11
Respectively to embodiment of the present invention catalyst and the desulfurization performance of comparative catalyst on the micro- anti-experimental provision of fixed bed
Evaluated.Loaded catalyst is 5g, and reaction is carried out in nitrogen atmosphere, and nitrogen flow is 30ml/min, and feedstock oil is used
Sulphur concentration is the catalytically cracked gasoline of 635 μ g/g, and wherein sulfur alcohol compound is 16 μ g/g, and thio-ether type compounds are 9.7 μ g/g,
The μ g/g of thiophane 27.3, thiophene and the μ g/g of alkylthrophene 572.3（Including thiophene, methylthiophene, ethylthiophene, dimethyl thiophene
Fen etc.）, the μ g/g of benzothiophene 9.7.320 DEG C of reaction temperature, feedstock oil weight space velocity 4 hours-1, the desulfurization degree and vapour of 1~6 hour
Oil yield the results are shown in Table 1, and the octane value changes before and after reaction are shown in Table 2.Wherein, the computational methods of desulfurization degree and product yield are such as
Under：
Desulfurization degree=100%-（Sulfur content after gasoline weight × reaction after reaction）/（Gasoline feeding amount × feed sulphur content）
×100%
Liquid product（Gasoline）Gasoline weight/gasoline feeding amount × 100% after yield=absorption
As seen from the data in Table 1, catalyst desulfurizing rate of the present invention is high, for desulfurization of hydrocarbon oil, liquid product high income.
Example 12
Desulfurization performance evaluation is carried out to catalyst B by the method for example 11, the difference is that first by catalyst hydrogen reducing
Be used further to desulphurization reaction, reducing condition is 360 DEG C, 4 hours, hydrogen volume air speed 1000 when-1.Desulfurization atmosphere is 93 volume % nitrogen
The gaseous mixture of gas and 7 volume % hydrogen.
The desulfurization degree of first 5 minutes of reaction is 100%, and desulfurization degree is 99.2% after reacting 1 hour.After reaction carries out 6 hours, urge
The desulfurization degree of agent still reaches 98%, and 6 hours yields of product liquid of absorption are 99.8%.Motor octane number increased 0.40
Unit, research octane number (RON) increased 0.38 unit, averagely increased 0.39 unit.
Example 13
This example investigates the regenerability of catalyst.
Catalyst A, D after inactivation is aoxidized 2 hours in 640 DEG C, air and is regenerated, then by the method for example 11
HDS evaluation is carried out, 2 are the results are shown in Table.
From table 2, performance can be recovered completely after catalyst regeneration of the present invention, and can still keep de- after repeatedly regeneration
Sulphur ability simultaneously improves product octane number.
Table 1
Table 2
△ MON represent the value added of product MON
△ RON represent the value added of product RON
Table 3
Liquid product yield in note * tables 1 and table 3 is the catalytic desulfurization yield of 6 hours.
Claims (14)
1. a kind of modified super-stable Y molecular sieves of desulfurization of hydrocarbon oil catalyst, including gallium and the metal oxidation with absorption sulfur functional
Thing, the modified super-stable Y molecular sieves of the gallium are the super-stable Y molecular sieves that gallium is mended through framework dealumination, the modified super steady Y of the gallium
The sial atomic molar ratio of type molecular sieve is 3.5~25, and silicon gallium atomic molar ratio is 4~90, and lattice constant is less than 2.46nm, institute
It is 15~98 that the modified super-stable Y molecular sieves of gallium are stated with the weight ratio of the metal oxide with absorption sulfur functional:2~85, institute
The metal oxide with absorption sulfur functional stated includes zinc oxide；Described catalyst includes what 20~75 weight % galliums were modified
Super-stable Y molecular sieves, the zinc oxide of 22~60 weight %, other metals with absorption sulfur functional of 0~30 weight % are aoxidized
Thing；
The preparation method of the catalyst, including：Formation includes the super-stable Y molecular sieves and zinc oxide component that the gallium is modified
The step of slurries, drying, roasting.
2. according to the catalyst described in claim 1, it is characterised in that described catalyst is modified including 20~75 weight % galliums
Super-stable Y molecular sieves, the zinc oxide of 22~60 weight %, 0~25 weight % other have absorption sulfur functional metal oxygens
Compound.
3. according to the catalyst described in claim 2, it is characterised in that described catalyst is modified including 25~70 weight % galliums
Super-stable Y molecular sieves, the zinc oxide of 25~55 weight %, 0~20 weight % other have absorption sulfur functional metal oxygens
Compound.
4. according to the catalyst described in claim 3, it is characterised in that the catalyst includes 0~40 weight in terms of aluminum oxide
Measure the modified super-stable Y molecular sieves of the al binder of %, in terms of oxide 0~40 weight % inorganic oxide matrix, and gallium and
The total content of the metal oxide with absorption sulfur functional is 50~100 weight %.
5. according to the catalyst described in claim 1, it is characterised in that the sial of the modified super-stable Y molecular sieves of the gallium is former
Sub- mol ratio is 5~25, and silicon gallium atomic molar ratio is 4~90, and specific surface area is 150~620m2/g。
6. according to the catalyst described in claim 1, it is characterised in that the super-stable Y molecular sieves that gallium is mended through framework dealumination
Preparation method it is as follows：The ammonium acetate aqueous solution that Y type molecular sieve raw material and concentration are 0.5~2.5mol/L is mixed, Ran Housheng
Temperature adds fluorine gallic acid ammonium salt solution to 70~90 DEG C, reacts 3~10h, and product after filtering, washes away the fluoride in product, obtains
Framework dealumination mends the super-stable Y molecular sieves of gallium.
7. according to the catalyst described in any one of claim 2~4, it is characterised in that other described have absorption sulfur functional
Metal oxide for Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, Ru, Rh, Pd, Ag, Cd, Au and Pt oxide in
One or more, zinc oxide is 1~20 with the weight ratio of other metal oxides with absorption sulfur functional:1.
8. according to the catalyst described in claim 4, it is characterised in that the al binder is in boehmite, Alumina gel
One or more；The inorganic oxide matrix is one or more in aluminum oxide, silica, amorphous silica-alumina, clay.
9. the preparation method of catalyst described in any one of claim 1~8, including：Formation includes the modified superstable gamma-type point of the gallium
The step of slurries, drying, roasting of son sieve and zinc oxide component.
10. in accordance with the method for claim 9, it is characterised in that the preparation method of the catalyst comprises the following steps：
A) gallium modified super-stable Y molecular sieves, zinc oxide component and water are beaten to form slurries；In the slurries with or without
Al binder component, with or without inorganic oxide matrix component；Described zinc oxide component is Zinc oxide powder and/or oxidation
Zinc precursor；
B) dry；
C) it is calcined.
11. in accordance with the method for claim 9, it is characterised in that the preparation method of the catalyst comprises the following steps：
A) by the modified super-stable Y molecular sieves of the gallium, zinc oxide component and water mashing；Described zinc oxide component is for before zinc oxide
Body, described zinc oxide precursor is the soluble-salt of zinc；
B) add precipitating reagent in slurries that step a) is obtained are dried, the consumption of precipitating reagent make the pH value of the slurries for obtaining for 7~
8, it is aging；Described precipitating reagent is one or more in ammoniacal liquor, carbonate solution, urea liquid；
C) slurries for obtaining step b) are directly filtered, washed and dried or introduce aluminum oxide in the slurries that step b) is obtained
Then binder component and/or the mashing of inorganic oxide matrix component are filtered, washed and dried；
D) the product roasting for obtaining step c).
12. in accordance with the method for claim 11, it is characterised in that the preparation method of the catalyst also includes step e)：
There is other of the product that step d) is obtained in addition to zinc oxide absorption sulfur functional aqueous metal solution to impregnate, dry, roasting.
A kind of 13. attached sulfur methods of hydrocarbon ils, including the step of gasoline is contacted with catalyst at 200~500 DEG C, its feature exists
In the catalyst that the catalyst is provided by any one of claim 1~8.
14. in accordance with the method for claim 13, it is characterised in that the temperature of the contact is 300~500 DEG C, contact
Pressure is 0.1~3.0MPa, and weight space velocity is 2~25h-1；Nitrogen, vapor, hydrogen, carbon monoxide, dioxy are introduced in contact
Change one or more diluent gas in the hydrocarbon gas and fluid catalytic cracking dry gas of carbon, boiling point less than 0 DEG C, the atmosphere of contact
Described in diluent gas proportion be 10~40 volume %.
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| CN108048129A (en) * | 2016-12-07 | 2018-05-18 | 郑州丽福爱生物技术有限公司 | A kind of selective desulfurization agent and its preparation method and application |
| CN106554803B (en) * | 2016-12-07 | 2018-02-27 | 宁夏瑞科新源化工有限公司 | A kind of gasoline desulfurizer and its preparation method and application |
| CN108085052A (en) * | 2016-12-07 | 2018-05-29 | 郑州丽福爱生物技术有限公司 | A kind of gasoline product desulfurizing agent and its preparation method and application |
| CN106694025B (en) * | 2017-01-17 | 2020-04-17 | 中国石油大学(北京) | Ultra-deep hydrodesulfurization catalyst carrier for poor diesel oil and preparation method and application thereof |
| CN110152596A (en) * | 2018-03-28 | 2019-08-23 | 山东联星能源集团有限公司 | A kind of petrol and diesel oil desulfurization rapidly agent |
| CN111085260A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Modified molecular sieve for hydrodesulphurization and preparation and application thereof |
| CN111085262A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Modified molecular sieve for hydrodesulphurization and preparation and application thereof |
| CN111085263A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Modified molecular sieve for hydrodesulphurization and preparation and application thereof |
| CN111085252A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Modified molecular sieve for hydrodesulphurization and preparation and application thereof |
| CN111111767A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN112316945B (en) * | 2020-11-03 | 2021-09-03 | 吉林大学 | Heterogeneous nano composite material, preparation method thereof, nitro reduction catalyst and application |
| CN114752404A (en) * | 2021-10-29 | 2022-07-15 | 中国石油大学(华东) | Method for light petroleum component photocatalytic oxidation desulfurization alcohol and hydrogen byproduct |
| WO2023197558A1 (en) * | 2022-04-12 | 2023-10-19 | 中国石油天然气股份有限公司 | Oil modification catalyst and preparation method therefor, oil modification method, and oil adsorptive desulfurization modification system |
| CN115253623B (en) * | 2022-08-22 | 2024-06-25 | 哈密市鲁江缘新材料有限公司 | Desulfurizing agent and preparation method and application thereof |
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