CN104148096B - A kind of dual metal reforming catalyst and preparation method thereof - Google Patents
A kind of dual metal reforming catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of dual metal reforming catalyst, comprise gamma-aluminium oxide carrier and the following active component of the content taking carrier as benchmark: platinum group metal 0.01～2.0 quality %, IV family metal 0.01～2.0 quality %, halogen 0.01～3.0 quality %, described gamma-aluminium oxide carrier is raw material preparation by sheet boehmite and strip boehmite, and its specific area is 160～250m2/ g, it is 0.65～0.9mL/g that mercury injection method is measured pore volume, the pore volume of determination of nitrogen adsorption is 0.40～0.60mL/g. This reforming catalyst has higher hydrothermal stability.
Description
Technical field
The present invention is a kind of catalyst for reforming naphtha and preparation method thereof, specifically, is that one contains expensiveDual metal reforming catalyst of metal and preparation method thereof.
Background technology
Naphtha reforming is important petroleum refining process, in a series of technology that relate in reformation, and catalystThe technology of core the most, the reactivity worth of reforming catalyst, intensity, the indexs such as hydrothermal stability all can be straightConnect the economic benefit that affects reformer operation. For continuous reformer, because catalyst is in device operationProcess in continuous regeneration always during this time, thereby the hydrothermal stability of catalyst seems particularly important. In phaseUnder biconditional operation condition, good hydrothermal stability means after catalyst experiences the identical regeneration period to haveHigher specific area, also just has the chlorine ability of better holding, and can reduce the injection rate of device running chlorine,Reduce the corrosion of chlorine to downstream. Under same operation condition, the catalyst that hydrothermal stability is high can have moreThe long cycle of operation, the economic benefit of raising device.
USP5298154 discloses a kind of reforming catalyst, and this catalyst contains the Pt of 0.2～0.4w%, 0.2～The second metal constituent element of 0.5w%, the chlorine of 0.5～1.5w%, adopts spherical gama-alumina as carrier, carriesBody has specific pore passage structure, has super big hole and the 5～20nm of the 200～10000nm linking togetherMesopore, under the condition of reorganization, the duct that is less than 15nm of determination of nitrogen adsorption is at least 80% of pore volume,This catalyst has good reforming activity and C5 +Selectively.
USP6514904 discloses a kind of Hydrocarban coversion catalysts, and this catalyst adopts a kind of special oxidationAlumina supporter, it is that the peak of 32.5 ° is at least 1.2 with the ratio of 34.0 ° of peak intensities that its XRD characterizes the 2 θ angles that obtain,And the peak that 2 θ angles are 46.0 ° mostly is 1.1 most with the ratio of 46.5 ° of peak intensities. But this patent does not relate to this equallyThe hydrothermal stability of catalyst carrier.
Because the hydrothermal stability of reforming catalyst depends primarily on carrier gama-alumina, thereby partial monopoly skillArt is directly involved in the raising of gama-alumina hydrothermal stability.
USP5837634 has proposed a kind of method of the aluminium oxide of preparing high hydrothermally stable, comprises to thin water aluminiumIn stone predecessor, add II A family or III B family metal cation, regulating pH is 3～9, is 70 DEG C in temperatureMore than process a period of time, change most boehmite into colloidal sol, colloidal sol is reclaimed to roastingBurn, obtain high hydrothermal stability aluminium oxide.
USP6773690 discloses aluminium oxide of a kind of high thermal stability and preparation method thereof, this aluminium oxideThe grain size that 020 crystal face records is greater than the grain size that 120 crystal faces record, and the crystal grain that 120 crystal faces are measured is largeSlight in 1.5nm, be preferably less than 0.5nm. Preparation process adopts aluminium alcoholates hydrolysis to prepare boehmite, and in70～110 DEG C long-time (24～70h) are aging, also can add the SiO of 0.1～5.0w%2，ZrO2，TiO2，B2O3Deng constituent element, the product finally obtaining has following feature: the grain size that 020 crystal face is measuredBe 6～10nm, pore volume is greater than 0.8mL/g, and specific area is 150～200m2/g。
US2006/0246000 discloses a kind of method of preparing high thermal stability aluminum oxide, and this aluminium oxide changesFor the temperature of Alpha-alumina exceedes 1300 DEG C, preparation process comprises that carrying out aluminium alcoholates hydrolysis prepares boehmite, waterSeparate process control pH higher than 8.5, hydrolytic process adds containing substituent carboxylic acid or carboxylate, boehmiteIn 80～250 DEG C of aging 2～20h, the control of ageing process solid content is 2～17w%, and the product obtaining presentsHigh heat endurance.
The above-mentioned method of preparing high hydrothermal stability gama-alumina all must add other metal constituent element, orPreparation process adds organic matter, so not only causes alumina production cost to increase, and adds other metal constituent elementAlso affect the purity of high-purity gama-alumina, during as carrier, affect the reactivity worth of catalyst.
Summary of the invention
The object of this invention is to provide a kind of dual metal reforming catalyst and preparation method thereof, this reforming catalystThere is higher hydrothermal stability.
Dual metal reforming catalyst provided by the invention, comprises gamma-aluminium oxide carrier and taking carrier as benchmarkThe following active component of content:
Platinum group metal 0.01～2.0 quality %,
IV family metal 0.01～2.0 quality %,
Halogen 0.01～3.0 quality %,
Described gamma-aluminium oxide carrier is raw material system by flaky crystalline grain boehmite and strip crystal grain boehmiteStandby, its specific area is 160～250m2/ g, it is 0.65～0.9mL/g that mercury injection method is measured pore volume, nitrogen absorptionThe pore volume that method is measured is 0.40～0.65mL/g.
The present invention prepares gamma-aluminium oxide carrier by flaky crystalline grain and strip crystal grain boehmite, makes the carrier makingMacropore and middle pore size distribution are more reasonable, and the bimetallic catalyst that thus prepared by carrier has higher hydrothermally stableProperty.
Brief description of the drawings
Fig. 1 is the TEM photo of the strip crystal grain boehmite prepared of the present invention.
Fig. 2 is the TEM photo of the flaky crystalline grain boehmite prepared of the present invention.
Detailed description of the invention
The present invention is that raw material is prepared gama-alumina and carried by flaky crystalline grain boehmite and strip crystal grain boehmiteBody, described sheet and strip crystal grain boehmite are by aluminium alcoholates (aluminum alkoxide) hydrolysis preparation. DescribedAluminium alcoholates makes by metallic aluminium and alcohol reaction, and strip crystal grain boehmite produces at aluminium alcoholates hydrolysis selfUnder the existence of alcohol, carry out that alcohol is mutually aging to be made, flaky crystalline grain boehmite, after aluminium alcoholates hydrolysis, separatesGo out aging making in the situation of alcohol. Two kinds of boehmites are all except reaction raw materials and product, additional without otherUnder the existence of component, make, have higher purity, gamma-aluminium oxide carrier purity prepared therefrom is high, andThere is suitable macropore (mercury injection method mensuration) and middle pore size distribution (determination of nitrogen adsorption), there is higher waterHeat endurance, the catalyst making thus also has higher hydrothermal stability, and catalyst is urged for naphthaAgent reforming reaction, can long time running and keep higher activity.
Active component content described in catalyst of the present invention is preferably:
Platinum group metal 0.1～1.0 quality %,
IV family metal 0.1～0.8 quality %,
Halogen 0.5～2.5 quality %.
Gamma-aluminium oxide carrier of the present invention is ball-aluminium oxide, preferably 1.4～2.2mm of its particle diameter.
Described platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, platinum, preferably platinum, and the preferred tin of IV family metal,The preferred chlorine of halogen.
Catalyst provided by the invention can have two kinds of preparation methods, and one is first to prepare gamma-aluminium oxide carrier, thenLoad active component, another kind is the gamma-aluminium oxide carrier of first preparing containing IV family metal, then load active component.
The first preparation method of described catalyst comprises by flaky crystalline grain boehmite and the thin water of strip crystal grainAluminium stone is that raw material is prepared gamma-aluminium oxide carrier, then by IV family metal compound solution dipping for gamma-aluminium oxide carrier,After dry, roasting, use again platinum group metal compounds solution impregnation, dry, roasting.
The second preparation method of described catalyst comprises by flaky crystalline grain boehmite and the thin water of strip crystal grainAluminium stone is the gamma-aluminium oxide carrier of raw material preparation containing IV family metal, then by the gamma-aluminium oxide carrier containing IV family metalUse platinum group metal compounds solution impregnation, dry, roasting.
The preferred tin of IV family metal described in above-mentioned preparation method.
The preparation method of described gamma-aluminium oxide carrier comprises flaky crystalline grain boehmite and the thin water aluminium of strip crystal grainStone mixes, and adds peptizing agent to make aluminium colloidal sol, and aluminium colloidal sol is dripped to ball forming, dry, roasting.
The preparation method of the described gamma-aluminium oxide carrier containing IV family metal comprises flaky crystalline grain boehmite and barShape crystal grain boehmite mixes, and adds peptizing agent to make aluminium colloidal sol, adds IV family metal in aluminium colloidal solCompound, then drip ball forming, dry, roasting.
In said method, while preparing carrier, the quality of flaky crystalline grain boehmite and strip crystal grain boehmiteThan being 10～90:10～90, preferably 30～70:30～70.
The peptizing agent of preparing aluminium colloidal sol is selected from inorganic acid, preferably hydrochloric acid or nitric acid, consolidating in the aluminium colloidal sol makingBody content of material is with Al2O3Count 10～40 quality %, preferably 15～25 quality %. In peptization course, addPreferably its halide, sulfate, oxalates, acetate or oxide of IV family metallic compound, preferredIV family metallic compound is SnCl2Or SnCl4。
Ball forming is dripped aluminium colloidal sol in the present invention in oil ammonia column. Concrete grammar is: aluminium colloidal sol is splashed into by upper strataIn the oil ammonia column of oil phase and lower floor's ammoniacal liquor composition, form spherical gel particles, then that wet bulb is old in ammoniacal liquorChange, the time is 1～30 hour, preferably 2～20 hours. Aging rear wet bulb is in 100～150 DEG C dry 2～8Hour, then carry out roasting. Roasting is carried out in moisture air, and sintering temperature is 400～800 DEG C, gasVolume space velocity 100～3000h-1, water in air content is 5～30 volume % preferably, and roasting time is 4～16Hour. Roasting can be carried out under same temperature, also can at multiple temperature, segmentation carry out. When baking inphases,Sintering temperature adopts the mode raising piecemeal to carry out, and rear one section of sintering temperature is higher than sintering temperature the last period,Roasting air air speed used also adopts the mode raising piecemeal to carry out, and water in air content adopts piecemeal and fallsLow mode is carried out.
When baking inphases, first paragraph sintering temperature be preferably 400～500 DEG C, gas volume air speed 100～500h-1, water in air content is 10～30 volume % preferably; Second segment sintering temperature be preferably 530～650 DEG C,Gas volume air speed 600～900h-1, water in air content is 7～9.5 volume % preferably; The 3rd section of sintering temperatureBe preferably 700～800 DEG C, gas volume air speed 950～1500h-1, water in air content preferably 1.0～6.5Volume %.
In above-mentioned oil ammonia column, ammonia spirit concentration is 3～15 quality % preferably, more preferably 5～12 quality %,Dripping ball process control oil ammonia column temperature is 10～40 DEG C, preferably 20～25 DEG C.
While dripping ball for reducing, produce emulsification at oil-water interfaces, preferably in aluminium colloidal sol, add relative colloidal sol quality to be1～10%, preferably 3～5% urea as stabilizing agent. Before dripping ball, preferably in oil ammonia column, add 10～50The relative solid butt of quality %(aluminium oxide) gasoline, diesel oil or kerosene.
The preparation method of strip crystal grain boehmite of the present invention comprises metallic aluminium and alcohol reaction, will reactThing is 80～120 DEG C of hydrolysis, directly by hydrolysate 100～150 DEG C aging, remove hydrolysis and generateAlcohol, residue is dry in 50～180 DEG C. The grain shape of strip crystal grain boehmite is bar shaped, crystal grainWide is 3～6nm, and length is 20～107nm.
The preparation method of described flaky crystalline grain boehmite comprises metallic aluminium and alcohol reaction, reactant is existed80～120 DEG C of hydrolysis, remove the alcohol in hydrolysate, and 40～150 DEG C aging, drier in 50～180 DEG C.The grain shape of flaky crystalline grain boehmite is tetragonal sheet, and its particle size is 3.5～8.0nm
In said method, the metallic aluminium of preparing aluminium alcoholates use can be aluminium bits, aluminium powder, aluminium shot, aluminium ingot etc.,Preferably aluminium bits or aluminium powder. The purity of metallic aluminium is higher than 99.0%, preferably higher than 99.9%, more preferably higher than99.99%, can ensure that like this product impurity content is low, reduce the step of impurity screening.
The described alcohol reacting with metallic aluminium is C3～C12Alcohol, preferred C5～C7Alcohol, the purity of alcohol usedBe not less than 98.0%, be preferably not less than 99.5%. The mol ratio of alcohol used and metallic aluminium is 4～10:1, excellentSelect 4～6:1. The reaction temperature of described alcohol and metallic aluminium is 40～200 DEG C, preferably 50～150 DEG C.
The method of aluminium alcoholates hydrolysis can be that aluminium alcoholates is splashed in water, also water can be splashed in aluminium alcoholates, alsoAluminium alcoholates and water can be added in hydrolytic tank simultaneously. Preferably 80～100 DEG C of the temperature of hydrolytic process, water/aluminium alcoholatesMol ratio is 3～6, preferably 4～6. Hydrolytic process should adopt stirring, and stir speed (S.S.) is 40～1000rpm, excellentSelect 100～400rpm.
Strip crystal grain boehmite of the present invention is by after aluminium alcoholates hydrolysis, under the existence of the alcohol producing in hydrolysisDirectly aging making, aging temperature is 100～380 DEG C, preferably 100～200 DEG C, aging pressure is0.1～2.0MPa, preferred 0.2～1.0MPa, the pressure that pressure can be produced by water vapour under high temperature in ageing tankRealize, preferably realize by being filled with inert gas, described inert gas is selected from nitrogen, helium or argon gas,Preferred nitrogen. Aging can carrying out under standing or stirring condition, preferably under agitation carries out, and stir speed (S.S.) is40～1000rpm, excellent 100～400rpm. Aging rear separation alcohol, the separation of alcohol can adopt decantation or moltenAgent extraction. Separation process repeatedly adds water in order to improve the rate of recovery of alcohol, can to adopt, repeatedly decantMethod. After dividing the slurry dried after alcohol, obtain the boehmite powder that crystal grain is strip.
Preparation and the said method of flaky crystalline grain boehmite are roughly the same, and different is first to separate hydrolysis to produceAlcohol carry out again agingly later, aging temperature is 40～380 DEG C, preferably 80～200 DEG C, then dry.
Above-mentionedly prepare the ageing time described in strip crystal grain boehmite and flaky crystalline grain boehmite methodBe 2～48 hours, preferably 2～24 hours, preferably 80～150 DEG C of baking temperatures, time be 2～24 hours,Preferably 3～12 hours.
In the preparation method of catalyst of the present invention, for gamma-aluminium oxide carrier, should first use IV family metallic compoundSolution impregnation is introduced IV family metal, then introduces platinum group metal. Described IV family metallic compound is selected from its halogenationThing, sulfate, oxalates, acetate or oxide, preferably IV family metallic compound is SnCl2Or SnCl4。For the gamma-aluminium oxide carrier containing IV family metal, directly introduce platinum group metal.
The described platinum group metal compounds of introducing platinum group metal for flooding is selected from chloroplatinic acid, ammonium choroplatinate, brominePlatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride two chlorocarbonyl platinum, dinitro diaminourea platinum or fourNitro sodium platinate. In the maceration extract of the platinum group metal of preparing, preferably add hydrochloric acid, to draw in catalystEnter halogen.
In catalyst preparation process, each dipping is introduced after metal component, and carrier all should be dried, roasting,Baking temperature is 50～300 DEG C, preferably 50～150 DEG C, and be 2～48 hours, preferably 4～16 drying timeHour. Sintering temperature is 370～700 DEG C, preferably 450～650 DEG C.
For ensureing that catalyst has suitable acidity, introducing behind platinum group metal the side that adopts water-halogen to regulateMethod is introduced enough halogens in catalyst. The method that water-halogen regulates is by halogen-containing and gas treatment waterCatalyst, preferably uses halogen-containing and air-treatment catalyst water. The temperature that water-halogen regulates is370～700 DEG C, preferably 450～650 DEG C, when adjusting, the mol ratio of institute's water and halogen is 10～100:1, excellentSelect 20～80:1, the adjusting time is 1～16h, preferred 2～8h.
Carry out water-halogen and regulate the described preferred chlorine of halogen, regulate the preferred Cl of chlorine-containing compound used2、HClMaybe can decomposite the organic compound of chlorine, as carrene, chloroform, carbon tetrachloride, dichloroethylene,Trichloro-ethylene, perchloroethylene, preferably dichloroethylene, perchloroethylene.
Catalyst of the present invention, after content of halogen has regulated, need reduce. Reduction is at substantially anhydrous ringUnder border, carry out, in reducing gases, water content requires to be less than 20ppm. Reducing gases can be H2, CO or other reductionGas, preferably H2, hydrogen can be pure hydrogen, can be also hydrogen and inert gas mist, describedInert gas preferred nitrogen, argon gas or helium. If mist, in gas, the volume of suitable hydrogen containsAmount is 1.0～99%, preferably 10～60%. Reduction temperature is 250～650 DEG C, preferably 400～600 DEG C, alsoThe former time is 0.5～16h, preferred 2～8h.
The method of carrying out naphtha catalytic reforming with catalyst of the present invention is included in 360～600 DEG C, preferred450～580 DEG C, 0.15～2.5MPa, preferred 0.15～1.0MPa, liquid volume air speed is 0.1～10h-1, excellentSelect 1～5h-1, hydrogen/hydrocarbon volume ratio is under 500～2000, preferably 700～1500 condition, makes naphtha and thisThe catalyst contact that invention provides.
Described feed naphtha can be straight-run naphtha, also can be hydrocracking naphtha, coking naphtha,Catalytic cracking naphtha or cracking of ethylene naphtha can be also the mixtures of above-mentioned raw materials. Naphtha oneAs contain alkane, cycloalkane and aromatic hydrocarbons, the carbon number of institute's hydrocarbonaceous is 5～12. Described raw material is according to ASTMThe initial boiling point that the method for D-86 is measured is 40～100 DEG C, preferably 70～90 DEG C, the end point of distillation be 140～220 DEG C,Preferably 160～180 DEG C.
Water content should be lower than 50ppm, preferably lower than 20ppm in the time entering reforming reaction district for feed naphtha.The dehydration of naphtha can adopt conventional adsorption dewatering, as adopted molecular sieve, aluminium oxide dehydration, also canCarry out suitable stripping operation by fractionating device and regulate, also can be by adsorption dry and the dry knot of gasClose the water of getting rid of in raw material.
Catalyst of the present invention preferably uses under without sulphur or low-sulfur environment, naphtha sulfur content less demanding in1.0 μ g/g, preferably higher than 0.5 μ g/g. In order to meet the requirements of sulfur content, naphtha can adopt various de-Sulphur method, comprises adsorption desulfurize, catalytic desulfurization.
Further describe the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare strip crystal grain boehmite.
(1) prepare aluminium alcoholates
In 15 liters of reactors of band stirring and condenser, adding 1628 grams of (1000ml) purity is 99.5%N-hexyl alcohol, 540 grams of aluminium powders that purity is 99.9%, are warming up to 120 DEG C, reaction cause after holding temperature be150 DEG C, continue to drip 6370 grams of (7830ml) n-hexyl alcohols, dropwise and continue reaction 1 hour, coolingTo 60 DEG C, obtain the solution containing n-hexyl alcohol aluminium.
(2) prepare boehmite
By the above-mentioned solution containing n-hexyl alcohol aluminium, at 85 DEG C, water/n-hexyl alcohol al mole ratio is 5, speed of agitator isUnder the condition of 150rpm, be hydrolyzed. Hydrolysis afterproduct is placed in to closed container, is filled with nitrogen to pressure0.62MPa, in 100 DEG C aging 3 hours, the speed of agitator of ageing process is 150rpm, passes through after agingDecantation separates the alcohol that hydrolysis produces, residue slurries in 120 DEG C dry 8 hours, obtain the thin water of strip crystal grainAluminium stone A, Fig. 1 is shown in by its TEM photo. As shown in Figure 1, the average length of strip boehmite crystal grain is80nm, wide is 5.2nm.
Example 2
Prepare flaky crystalline grain boehmite.
By example 1(1) method of step prepares n-hexyl alcohol aluminium and is hydrolyzed by (2) one step process, will be hydrolyzedAlcohol in product separates by decant, and residue slurries are placed in closed container, then are filled with nitrogen to pressure0.62MPa, in 80 DEG C aging 6 hours, the speed of agitator of ageing process is 150rpm. Aging afterproduct in120 DEG C are dried 8 hours, obtain flaky crystalline grain boehmite B, and Fig. 2 is shown in by its TEM photo. Can by Fig. 2Know, the average crystal grain granularity of flaky crystalline grain boehmite is 4.5nm.
Example 3
Prepare catalyst of the present invention.
(1) prepare spherical gamma-aluminium oxide carrier.
Get 60 grams of strip crystal grain boehmite A, 140 grams of flaky crystalline grain boehmite B, add 400 grams denseDegree is the nitric acid of 1.7 quality %, 5.1g urea, the SnCl of 33.3 grams of kerosene and scheduled volume4, so that gamma oxidationAluminium is that the Sn content of benchmark is 0.3 quality %, stirs 1 hour, makes aluminium colloidal sol, wherein with Al2O3The solid substance concentration of meter is 15 quality %.
Above-mentioned aluminium colloidal sol is splashed into the upper oil phase and the 200 centimetres of lower floors that are made up of the normal octane of 2.5 millimeters denseDegree is in the oil ammonia column of ammonia spirit composition of 8 quality %, forms spherical gel particles. Drip ball process controlOil ammonia column temperature is 23 DEG C. Wet bulb in ammoniacal liquor aging 3 hours, then filters, with deionized water rinsing 3Inferior, 60 DEG C are dried 6 hours, and 120 DEG C are dried 10 hours.
After being dried, bead is at 450 DEG C, and gas volume air speed is 500h-1, water content is the sky of 10 volume %In gas, process 4 hours; In 600 DEG C, gas volume air speed is 800h again-1, water content is 7.5 volume %'sIn air, process 3 hours; And then in 750 DEG C, gas volume air speed is 1000h-1, water content is 5.0In the air of volume %, process 1.0 hours, obtain spherical gamma-aluminium oxide carrier C, its physical property is in table 1,Wherein crushing strength is measured by ASTMD4179-2011 method, lower same.
(2) prepare continuous reforming catalyst
Get 100g support C, with the mixed liquor dipping of chloroplatinic acid and hydrochloric acid, the platinum content in mixed liquor should makeIn the catalyst making, platinum content is 0.35 quality %, and the amount that contains HCl is divided with respect to butt quality of aluminaNumber is 2.2%. Gu the liquid/mass ratio of maceration extract and carrier is 1.8, dip time is 12 hours. After dippingThe air-treatment that gained solid is 60:1 in 510 DEG C of water/cl molar ratios 8 hours, then in 500 DEG C with pureHydrogen reduction makes catalyst E, and its composition is in table 2.
Example 4
Press the method Kaolinite Preparation of Catalyst of example 3, when (1) step that different is is prepared carrier, get 140 grams of stripsCrystal grain boehmite A, 60 grams of flaky crystalline grain boehmite B mix, after a ball forming, make spherical gamma-Alumina support D, its physical property is in table 1. The catalyst F being prepared by (2) one step process by carrier DComposition in table 2.
Example 5
Press the method Kaolinite Preparation of Catalyst of example 3, different is that (1) step will be dried rear bead in 650 DEG C, gasBody volume space velocity is 1000h-1, water content is to process 6 hours under the condition of 10 volume %, obtains gamma oxidationAlumina supporter G, its physical property is in table 1. The group of the catalyst H being prepared by (2) one step process by carrier GPrejudice table 2.
Example 6
Press the method Kaolinite Preparation of Catalyst of example 3, when (1) step that different is is prepared carrier, get 140 grams of stripsCrystal grain boehmite A, 60 grams of flaky crystalline grain boehmite B mix, drip after ball forming, by dried pellet in650 DEG C, gas volume air speed is 1000h-1, water content is to process 6 hours under the condition of 10 volume %,To gamma-aluminium oxide carrier I, its physical property is in table 1. The catalyst J being prepared by (2) one step process by carrier IComposition in table 2.
Comparative example 1
Press the method Kaolinite Preparation of Catalyst of example 3, (1) step that different is is used 200 grams of bars while preparing carrierShape crystal grain boehmite A makes carrier K after dripping ball forming, and its physical property is in table 1. By carrier KThe composition of the catalyst L preparing by (2) one step process is in table 2.
Comparative example 2
Press the method Kaolinite Preparation of Catalyst of example 3, (1) step that different is is used 200 grams of sheets while preparing carrierShape crystal grain boehmite B makes carrier M after dripping ball forming, and its physical property is in table 1. By carrier KThe composition of the catalyst n of preparing by (2) one step process is in table 2.
Example 7～12
Following instance is evaluated the hydrothermal stability of catalyst of the present invention.
Get 50g catalyst, at 700 DEG C, gas volume air speed is 1000h-1Condition under, with water content beThe air of 20 volume % is processed respectively 6 hours, and 12 hours, 18 hours, 30 hours, 42 hours, 60 is littleTime, 80 hours, 100 hours, the specific area of mensuration different disposal time period catalyst, investigated its hydro-thermalStability. Each example used catalyst and respectively process time period specific area value in table 3.
From table 3 data, catalyst of the present invention, than comparative catalyst, passes through long hydrothermal treatment consists,Specific area fall is less, illustrates that catalyst iterative regenerable of the present invention uses the long period.
Table 1
Table 2
Table 3
Example 13～18
In reforming catalyst evaluating apparatus, pack 50mL catalyst into, taking naphtha shown in table 4 as reactionRaw material, at 530 DEG C, 0.7MPa, feed volume air speed 2h-1, hydrogen/hydrocarbon volume ratio condition that is 1000:1Lower reaction 120 hours, each example used catalyst and average response result data are in table 5, and wherein carbon deposit isReact the carbon deposit content in 120 hours rear catalysts.
Adopt RIPP107-90 method (" the Petrochemical Engineering Analysis method " of writing referring to Yang Cuiding etc.) to catalysisAgent coke content is measured, and evaluation instrument used is that the EMIA-820V type of Japanese HORIBA company is infraredSulphur charcoal analyzer.
As shown in Table 5, than comparative catalyst, the coke deposit rate of catalyst of the present invention obviously reduces, thisBright catalyst has good reactivity worth.
Table 4
Table 5
Claims (16)
1. a dual metal reforming catalyst, comprises gamma-aluminium oxide carrier and containing taking carrier as benchmarkMeasure following active component:
Platinum group metal 0.01～2.0 quality %,
Tin 0.01～2.0 quality %,
Halogen 0.01～3.0 quality %,
Described gamma-aluminium oxide carrier is raw material system by flaky crystalline grain boehmite and strip crystal grain boehmiteStandby, its specific area is 160～250m2/ g, the pore volume that mercury injection method is measured is 0.65～0.9mL/g, nitrogen is inhaledThe pore volume that attached method is measured is 0.40～0.65mL/g,
The preparation method of described strip crystal grain boehmite comprises metallic aluminium and alcohol reaction, reactant is existed80～150 DEG C of hydrolysis, directly by hydrolysate 100～150 DEG C aging, then remove hydrolysis generate alcohol,Residue slurries in 100～180 DEG C dry, the described alcohol reacting with metallic aluminium is C3～C12Alcohol;
The preparation method of described flaky crystalline grain boehmite comprises metallic aluminium and alcohol reaction, reactant is existed80～150 DEG C of hydrolysis, remove the alcohol in hydrolysate, and 40～150 DEG C aging, and 100～180 DEG C dry, instituteStating the alcohol reacting with metallic aluminium is C3～C12Alcohol.
2. according to catalyst claimed in claim 1, it is characterized in that described active component content is:
Platinum group metal 0.1～1.0 quality %,
Tin 0.1～0.8 quality %,
Halogen 0.5～2.5 quality %.
3. according to the catalyst described in claim 1 or 2, it is characterized in that described gamma-aluminium oxide carrierFor spherical, its particle diameter is 1.4～2.2mm.
4. according to the catalyst described in claim 1 or 2, it is characterized in that described platinum group metal is platinum,Halogen is chlorine.
5. according to catalyst claimed in claim 1, it is characterized in that the described alcohol reacting with metallic aluminiumFor C5～C7Alcohol.
6. according to catalyst claimed in claim 1, it is characterized in that described ageing time is 2～24 littleTime, be 2～24 hours drying time.
7. a preparation method for catalyst described in claim 1, comprise by flaky crystalline grain boehmite andStrip crystal grain boehmite is that raw material is prepared gamma-aluminium oxide carrier, then gamma-aluminium oxide carrier is molten with tin compoundImmersion stain, uses platinum group metal compounds solution impregnation, dry, roasting after dry, roasting again.
8. a preparation method for catalyst described in claim 1, comprise by flaky crystalline grain boehmite andStrip crystal grain boehmite is that raw material is prepared stanniferous gamma-aluminium oxide carrier, then by stanniferous gamma-aluminium oxide carrierUse platinum group metal compounds solution impregnation, dry, roasting.
9. it is characterized in that in accordance with the method for claim 7, preparation method's bag of gamma-aluminium oxide carrierDraw together flaky crystalline grain boehmite and strip crystal grain boehmite mixed, add peptizing agent to make aluminium colloidal sol,Aluminium colloidal sol is dripped to ball forming, dry, roasting.
10. it is characterized in that in accordance with the method for claim 8, the preparation of stanniferous gamma-aluminium oxide carrierMethod comprises flaky crystalline grain boehmite and strip crystal grain boehmite is mixed, and adds peptizing agent to makeAluminium colloidal sol adds tin compound in aluminium colloidal sol, then drips ball forming, dry, roasting.
11. in accordance with the method for claim 10, it is characterized in that described tin compound is SnCl2OrSnCl4。
12. according to the method described in claim 9 or 10, it is characterized in that the solid of described aluminium colloidal solContent of material is with Al2O3Count 10～40 quality %.
13. according to the method described in claim 7 or 8, it is characterized in that the described thin water aluminium of flaky crystalline grainThe preparation method of stone comprises metallic aluminium and alcohol reaction, reactant, 80～150 DEG C of hydrolysis, will be hydrolyzed to productAlcohol in thing is removed, and 40～150 DEG C aging, and 100～180 DEG C dry, and the described alcohol reacting with metallic aluminium is C3～C12Alcohol;
The preparation method of described strip crystal grain boehmite comprises metallic aluminium and alcohol reaction, reactant is existed80～150 DEG C of hydrolysis, directly by hydrolysate 100～150 DEG C aging, then remove hydrolysis generate alcohol,Residue slurries in 100～180 DEG C dry, the described alcohol reacting with metallic aluminium is C3～C12Alcohol.
14. in accordance with the method for claim 13, it is characterized in that the described alcohol reacting with metallic aluminiumFor C5～C7Alcohol.
15. according to the method described in claim 9 or 10, it is characterized in that dried carrier 400～800 DEG C, water content is to carry out hydrothermal treatment consists, gas volume air speed when processing in the air of 5～30 volume %It is 100～3000 hours-1。
16. according to the method described in claim 7 or 8, it is characterized in that described platinum group metal compoundsBe selected from chloroplatinic acid, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride two chloroformylsBase platinum, dinitro diaminourea platinum or tetranitro sodium platinate.
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