CN1393514A - Dual-function reforming catalyst containing Pt and Sn and its preparing process - Google Patents
Dual-function reforming catalyst containing Pt and Sn and its preparing process Download PDFInfo
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- CN1393514A CN1393514A CN 02100226 CN02100226A CN1393514A CN 1393514 A CN1393514 A CN 1393514A CN 02100226 CN02100226 CN 02100226 CN 02100226 A CN02100226 A CN 02100226A CN 1393514 A CN1393514 A CN 1393514A
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Abstract
A reforming bimetal catalyst for naphtha contains alumina as carrier, Pt (0.01-2.0 m%), IVA femily metal (0.01-5.0), P (0.01-10) and haloid element (0.1-10). It has high selectivity to arylhydrocarbon.
Description
Technical field
The present invention is dual-function reforming catalyst and preparation method.Specifically, be a kind of catalyzer and preparation method who loads on the platiniferous tin on the porous support.
Background technology
Catalytic reforming is one of important production technique of refining of petroleum, and its main purpose is to produce stop bracket gasoline, aromatic hydrocarbons and by-product hydrogen.At present, the reforming catalyst of industrial widespread use mostly is dual metal reforming catalyst, mainly contains Pt-Re, Pt-Sn two big series.With respect to the Pt-Re catalyzer, the Pt-Sn catalyzer has preferably low pressure stability and higher arenes selectivity, and catalyzer do not need prevulcanized, more is applicable to continuous reforming process.
Reforming catalyst is the dual-function catalyst with isomerization acidity and hydrogenation-dehydrogenation functionality, its isomerization acid function is provided by acid inorganic oxide carrier of porous such as aluminum oxide, for increasing acidity of catalyst to reach the requirement of reforming reaction, usually to wherein adding the halogen adjustment of acidity.Hydrogenation-the dehydrogenation functionality of catalyzer then by VIII family metal, provides as platinum or palladium.The adding of the second metal constituent element Re or Sn can make activity of such catalysts stability improve greatly, and reduces the consumption of precious metal.
In catforming process, several competing reactions take place simultaneously.These reactions comprise that cyclohexane dehydrogenation becomes aromatic hydrocarbons, alkyl cyclopentane dehydroisomerization to turn to aromatic hydrocarbons, and dehydrating alkanes is cyclized into aromatic hydrocarbons, paraffinic hydrocarbons hydrocracking becomes C
1～C
3The isomerization of taking off alkyl and paraffinic hydrocarbons of light hydrocarbon product, alkylbenzene.In these reactions, because hydrocracking produces the yield that light hydrocarbon gas can reduce gasoline, particularly bimetallic catalyst such as Pt-Re, Pt-Sn has stronger lytic activity than single platinum catalyst.For reducing the lytic activity of catalyzer, the normal method that adopts is that adding the 3rd, the 4th kind of constituent element improve catalyst performance in bimetallic catalyst, improves selectivity.
USP3,770,616 disclose a kind of reforming catalyst, this catalyzer comprises that the lead and 0.01～10.0 of Pt, 0.01～5.0 heavy % of 0.01～5.0 heavy % weighs a kind of element in institute's column element that is selected from of %, and optionally element comprises Cu, Ag, Au, B, Tl, Ti, Zr, V, Ta, Mn, Fe, Co, Ni, Th, Y, P, Sb, Ce, Sc, Ga, In, Hf and Nb.Support of the catalyst comprises aluminum oxide, silicon oxide, silica-alumina and zeolite.
USP4,416,804 pairs of Pt-Sn catalyzer improve, and to wherein adding cobalt and phosphorus constituent element, and think that the bound energy of phosphide and cobalt improves selectivity of catalyst and activity stability in the catalyzer.Platinum content is 0.01～2.0 heavy % in this catalyzer, and tin content is 0.01～5.0 heavy %, and cobalt contents is 0.5～5.0 heavy %, and phosphorus content is 0.01～5.0 heavy %, and content of halogen is 0.1～3.0 heavy %.Wherein the atomic ratio of tin and platinum is 0.1～13: 1, and the atomic ratio of cobalt and platinum is 0.15～66: 1.The compound of introducing the adding of phosphorus constituent element in catalyzer is selected from P contained compounds such as Hypophosporous Acid, 50 (hypophosphorous acid), phosphoric acid, phosphorous acid-dimethyl esters, triphenylphosphine, phosphorus trichloride.
USP4,426,279 disclose the preparation method of the reforming catalyst of a kind of platiniferous and phosphorus, contain the platinum of 0.01～5.0 heavy %, phosphorus and the chlorine of 0.01～5.0 heavy % and the alumina supporter of surplus of 0.01～5.0 heavy % in the catalyzer of this patent disclosure.Its improvements are impregnation sequences of active component, promptly introduce earlier platinum in carrier, and then introduce the phosphorus constituent element.The catalyzer that makes like this is than while introducing platinum and phosphorus in carrier, or elder generation's introducing phosphorus, and the catalyzer that the method for back introducing platinum makes has higher C5
+Productive rate and more hydrogen output.
Summary of the invention
The purpose of this invention is to provide a kind of dual-function reforming catalyst of platiniferous tin of modification, this catalyzer has good selectivity and activity stability.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
We find, add the phosphorus constituent element in platinum tin reforming catalyst, can improve selectivity of catalyst, reduce coke deposit rate, thereby improve gasoline and/or aromatics yield.This catalyzer is specially adapted to comprise C
6～C
8The petroleum naphtha of hydro carbons is the catforming process of raw material production aromatic hydrocarbons.
Description of drawings
Fig. 1, Fig. 2 are catalyzer of the present invention and contrast medium selectivity of catalyst comparing result.
Embodiment
Reforming catalyst provided by the invention comprises alumina supporter and active ingredient composed as follows, and described each active ingredient is all in element, and its content serves as to calculate benchmark with the butt aluminum oxide,
Platinum 0.01～2.0m%
Metal 0.01～the 5.0m% of IVA family
Phosphorus 0.01～10.0m%
Halogen 0.1～10.0m%
The preferred content of above-mentioned each active ingredient is:
Platinum 0.05～1.0m%
Metal 0.1～the 2.0m% of IVA family
Phosphorus 0.05～5.0m%
Halogen 0.1～3.0m%
Described IVA family metal is selected from, preferred tin, the preferred chlorine of halogen.
The atomic ratio of phosphorus and platinum is 0.5～20: 1 in the catalyzer, preferred 1～10: 1; The atomic ratio of phosphorus and tin is 0.2～15.0: 1, preferred 0.5～10.0: 1.
The mean pore size of described alumina supporter is that 20～300 , pore volume are that 0.2～1.0ml/g, specific surface area are 100～500m
2/ g.Preferably the aluminium hydroxide by aluminum alkoxide hydrolysis by-product makes high-purity gama-alumina.Described aluminum alkoxide can be the high-carbon aluminum alkoxide that contains four above carbon atoms, also can be the low-carbon alkoxy aluminium that is less than four carbon atom.
The shape of carrier can be ball-type, excellent type, ball, bead, sheet, the granular or cylindricality extruded, preferred ball-type.
Method for preparing catalyst provided by the invention comprises the steps:
(1) with aluminium hydrate powder making beating, acidifying, the solubility IVA family metallic compound that adds predetermined amount stirred 0.5～4.0 hour with the urea that accounts for aluminium hydrate powder weight 20～40%, adding accounts for the kerosene of aluminium hydrate powder weight 0 or 10～40% again, 2～6% fatty alcohol-polyoxyethylene ether stirred 0.5～4.0 hour, drip ball forming then, dry back obtains containing the carrier of IVA family metal in 370～600 ℃ of roastings
(2) with soaking altogether or the method for step impregnation is introduced platinum and phosphorus in the carrier that contains IVA family metal,
(3), in 315～650 ℃ of hydrogen, reduced 0.5～10.0 hour with after solid drying, the roasting behind the above-mentioned dipping.
(1) step is the stanniferous alumina supporter of preparation in the aforesaid method, and the amount of the institute's water of wherein aluminium hydrate powder being pulled an oar is 1.5～2.5 times of aluminium hydrate powder weight, so that the solid-liquid weight ratio is 1.5～2.5: 1, and preferred 1.8～2.0: 1.Carry out acidifying after the aluminium hydrate powder pulp again, acidifying acid is selected from nitric acid or hydrochloric acid, and the add-on of acid is 2～15% of an aluminium hydrate powder weight, adds slurries again after the acid of adding is preferably diluted.The high purity aluminium hydroxide powder that the preferred aluminum alkoxide hydrolysis of described aluminium hydrate powder makes.
Can add solubility IVA family metallic compound after the above-mentioned slurries acidifying, also need add urea simultaneously, preferred 1～3 hour of churning time in stirring at room.IVA family metallic compound is selected from tetrem alkoxide, germanium tetrachloride, lead nitrate, lead acetate or the lead chlorate of tin protobromide, tin protochloride, tin tetrachloride, stannic chloride pentahydrate, germanium dioxide, germanium, preferred tin protochloride, tin tetrachloride or stannic chloride pentahydrate.
After in the acidifying slurries, adding IVA family metallic compound, add kerosene and fatty alcohol-polyoxyethylene ether again, preferred 0.5～1.0 hour of churning time, its effect is the aperture that increases carrier.Drip ball forming with conventional method in oil ammonia column or deep fat post then, in ammoniacal liquor aging 0.5～36 hour then, preferred 20～24 hours, 100～120 ℃ of dryings 8～24 hours promptly got stanniferous alumina supporter after the roasting.Preferred 550～650 ℃ of maturing temperature, preferred 4～10 hours of time.
Other active ingredient in the catalyzer of the present invention beyond the detin all can be introduced carrier by dipping method.(2) going on foot described method is at the carrier that contains IVA family metal, particularly introduces platinum constituent element and phosphorus constituent element in the stanniferous carrier, and the method for introducing can be the method for soaking altogether, also can be branch and soaks method.The method of soaking is with containing the carrier that solution impregnation that platinic compound and P contained compound be made into contains IVA family metal, dry roasting altogether.Dividing the method for soaking is the carrier that contains IVA family metal earlier with the platiniferous solution impregnation, and the P contained compound solution impregnation is used in drying, roasting again, dry then, roasting.Divide to soak also and can introduce the phosphorus constituent element earlier, introduce the platinum constituent element again, only to need after the drying be available platiniferous solution impregnation but draw behind the phosphorus carrier.Each dipping back carrier drying temperature is 60～200 ℃, and the time is 4～20 hours, preferred 400～700 ℃ of maturing temperature, preferred 1～20 hour of time.
In the catalyzer process, the carrier behind the last impregnation drying is just introduced the roasting of the carrier of phosphorus and platinum and is preferably adopted water chlorine treatment process to carry out roasting, promptly adds certain amount of H Cl and water vapor in the process of roasting, with the chlorine in the make-up catalyst.Water chlorine treatment process be with carrier in air, in 370～600 ℃, H
2Handle preferred 370～700 ℃ of treatment temp, preferred 0.5～5.0 hour of time under the condition of O/HCl mol ratio 1.0～150: 1.If adopt step impregnation method, then water chlorine is handled the last time and is carried out behind the impregnated carrier.
The steeping fluid of preparing in the above-mentioned steeping process is 1.0～5.0: 1 with the liquid/solid volume ratio of carrier, preferred 1.5～2.5: 1.Dipping temperature is 10～100 ℃, and the time is 1.0～20.0 hours.The platinic compound that contains that steeping fluid uses is selected from Platinic chloride, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, Tetrachloroplatinum hydrate, dichloride two chloroformyl platinum, dinitrobenzene diamino platinum, tetranitro sodium platinate (sodium tetranitroplatinate), preferred Platinic chloride.For the benefit of the introducing of halogen component and the metal component uniform distribution on whole carrier generally adds competitive adsorbate in the dipping solution.Preferred competitive adsorbate is HCl or trichoroacetic acid(TCA), and both can add steeping fluid respectively, preferably both are added steeping fluid simultaneously.The weight ratio of HCl and trichoroacetic acid(TCA) is 0.01～100: 1 in the steeping fluid, preferred 0.1～10: 1, and the concentration of competitive adsorbate in steeping fluid counts 0.2～5.0% with chlorine, and preferred 0.8～3.0%.If adding trichoroacetic acid(TCA) is competitive adsorbate, after the carrier drying, be preferably in 190～230 ℃ of heating 0.5～10 hour, in the steeping fluid so that the trichoroacetic acid(TCA) desorption.
Phosphorus constituent element in the catalyzer is introduced carrier by the steeping fluid of P contained compound preparation, and the amount of phosphorus compound should make wherein phosphorus content reach the requirement of catalyzer in the steeping fluid.The phosphorus compound of preparation steeping fluid is selected from phosphoric acid, triphosphopyridine nucleotide, triphenylphosphine, phosphorus trichloride, phosphoric acid, tributyl phosphorus oxide, tributyl phosphate, phosphorus tribromide, triiodo phosphorus oxide or phosphoryl chloride, preferably phosphoric acid, triphenylphosphine, phosphorus trichloride or phosphorus tribromide, more preferably phosphoric acid.
Above-mentioned P contained compound can contain platinic compound with Platinic chloride etc. and be mixed with steeping fluid, utilizes the method for soaking altogether to introduce platinum and phosphorus simultaneously in carrier, will flood afterwards solid drying, roasting then.Also the phosphorus constituent element can be introduced separately into carrier,, again phosphorus compound be mixed with steeping fluid dipping platiniferous carrier as in the stanniferous carrier, introducing platinum earlier; Also can be to soak phosphorus earlier, after soak platinum.Above-mentioned branch soaks in the process, soak platinum after carrier preferably pass through roasting, with prevent platinum in follow-up dipping by wash-out.In addition, the phosphorus constituent element can also be introduced carrier by co-precipitation, common agglomerative method.
The reductive purpose was that the platinum constituent element is reduced into metallic state during (3) went on foot in the described method, and guaranteed that it is distributed on the carrier equably.Reduction needs to carry out preferred 400～600 ℃ of reduction temperature, preferred 0.5～5.0 hour of time under substantially anhydrous condition.Reducing gas also can be selected other reducing gass such as CO for use except that hydrogen.If in the preparation process, the phosphorus constituent element is introduced after the platinum constituent element, and platinum is reduced, when then introducing phosphorus with pentavalent phosphorous compound solution such as phosphoric acid, also needs reduce to phosphorus again.
Catalyzer of the present invention is suitable for catalytic reforming reaction.Reformer feed is the whole-distillate gasoline of 40～220 ℃ of boiling ranges, the mixture of forming as the gasoline of straight run and pressure gasoline or its admixture heat cracking or catalytic cracking, part reformed naphtha or dehydrogenation petroleum naphtha.The processing condition that catalyzer of the present invention is suitable for are absolute pressure 100KPa～7.0MPa, preferred 350～2500KPa, 315～600 ℃ of temperature, preferred 425～565 ℃, hydrogen/hydrocarbon mol ratio 1～20, preferred 2～10, feeding liquid hourly space velocity (LHSV) 0.1～10.0 o'clock
-1, preferred 1.0～5.0 o'clock
-1
Reforming reaction needs to carry out under substantially anhydrous condition.The water content of raw material when entering reaction zone should be less than 50ppm, preferably less than 20ppm.Water in the reformer feed can carry out drying as molecular sieve by conventional sorbent material, also can carry out suitable stripping by fractionation plant and operate and regulate.Also the gentle soma constipation of adsorption dry can be got rid of altogether the water in the raw material.In like manner, require to enter that water-content should be less than 20ppm in the hydrogen stream of reaction zone, suitable water-content is 10～20ppm.
Catalyzer of the present invention uses under no sulphur environment.The feed naphtha desulfurization can adopt any ordinary method to carry out, as adopting adsorption desulfurize, catalytic desulfurization etc.Adsorption desulfurize can adopt the SiO of molecular sieve, crystal aluminosilicate, high-specific surface area
2-Al
2O
3, material such as gac.Catalytic desulfurization can adopt methods such as conventional hydrofining, hydrotreatment, hydrogenating desulfurization.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare catalyzer of the present invention.
(1) prepares stanniferous alumina supporter
Get 100 gram SB aluminium hydrate powder (Germany, Condea company) and an amount of deionized water, Gu making liquid/weight ratio is 2.0, stirring makes its pulp, the adding volume ratio is 1: 1 a nitric acid (analytical pure, Shunyi, Beijing Lee satisfies the chemical plant), its add-on is 7.5 milliliters/100 gram SB powder, add 30 gram urea (analytical pure simultaneously, the Beijing Chemical Plant) and the tin protochloride (chemical pure of predetermined amount, Red Star chemical plant, Beijing) hydrochloric acid (analytical pure, the Beijing Chemical Plant) solution, the content that makes Sn in the solution are 0.30m% (is benchmark with the butt aluminum oxide), stir 1 hour, add 30 gram kerosene and 3 gram fatty alcohol-polyoxyethylene ether (auxiliary reagent factory, Tianjin) stirrings 1 hour then, in oil ammonia column, drip ball forming.Wet bulb wore out 1 hour in ammoniacal liquor (analytical pure, the new Photochemical agents in Beijing factory), filtered then, with deionized water flushing 2～3 times, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 10 hours, the 600 ℃ of roastings 4 hours in dry air of dried ball, gas agent volume ratio is 700, obtains containing the carrier of Sn.
(2) preparation catalyzer
Above-mentioned stanniferous carrier was flooded 24 hours at 25 ℃ with 180 milliliters of solution that contain 0.33m% Platinic chloride, 0.18m% phosphoric acid (analytical pure, Beijing Chemical Plant), 0.67m%HCl and 2.8m% trichoroacetic acid(TCA), and the liquid during dipping/solid volume ratio is 1.8.220 ℃ of heating made the trichoroacetic acid(TCA) desorption in 4 hours.Filter, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 10 hours, then in air, activation treatment is 6 hours under 510 ℃, 60: 1 condition of water/cl molar ratio.
(3) catalyst reduction
With the carrier that makes of (2) step, 500 ℃ with hydrogen reducing 4 hours, obtains catalyst A, and its composition sees Table 1, and each active component content serves as to calculate benchmark with the butt aluminum oxide.
Example 2
Method according to example 1 prepares the spherical carrier of the aluminum oxide that contains Sn, introduces platinum and phosphorus with the method for soaking altogether then, and different is the phosphoric acid that contains 0.53m% in the steeping fluid of preparing in (2) step.The composition that makes catalyst B sees Table 1.
Example 3
Method according to example 1 prepares the spherical carrier of the aluminum oxide that contains Sn, introduces platinum and phosphorus with the method for soaking altogether then, and different is the phosphoric acid that contains 1.05m% in the steeping fluid of preparing in (2) step.The composition that makes catalyzer C sees Table 1.
Example 4
Method according to example 1 prepares the spherical carrier of the aluminum oxide that contains Sn, floods these carriers 24 hours with 180 milliliters of trichoroacetic acid(TCA) solution that contain Platinic chloride, 0.67m%HCl and the 2.8m% of 0.33m% at 25 ℃ then, and the liquid during dipping/solid volume ratio is 1.8.120 ℃ of dryings 6 hours, 220 ℃ of heating made the trichoroacetic acid(TCA) desorption in 4 hours.Roasting is 4 hours in 510 ℃ of air.Again with carrier after the roasting with dipping under 180 milliliters of phosphoric acid solution room temperatures that contain 0.53m% 24 hours, 120 ℃ of dryings 6 hours, afterwards in air, activation treatment is 6 hours under 510 ℃, 60: 1 condition of water/cl molar ratio.500 ℃ with hydrogen reducing 4 hours, obtains catalyzer D, and its composition sees Table 1.
Example 5
Method substep in the stanniferous carrier by example 4 is introduced platinum constituent element and phosphorus constituent element, and reduces.Different is earlier with flooding stanniferous alumina supporter under 180 milliliters of phosphoric acid solution room temperatures that contain 0.53m%, 120 ℃ of dryings 6 hours, and then with 180 milliliters of these carriers of solution impregnation that contain 0.33m% Platinic chloride, 0.67m%HCl and 0.28m% trichoroacetic acid(TCA), 120 ℃ of dryings 6 hours, 220 ℃ of heating made the trichoroacetic acid(TCA) desorption in 4 hours.Afterwards in air, activation treatment is 6 hours under 510 ℃, 60: 1 condition of water/cl molar ratio.500 ℃ with hydrogen reducing 4 hours, obtains catalyzer E, and its composition sees Table 1.
Comparative Examples 1
The preparation active ingredient is the spherical catalyst of Pt, Sn.
Method according to example 1 prepares comparative catalyst F, and different is that used steeping fluid of (2) step is not phosphorous, and the composition of catalyzer F sees Table 1.
Comparative Examples 2
With reference to USP4,416,804 method prepares comparative catalyst H.
Contain the Sn carrier by the preparation of the method for example 1, after 3 hours, the liquid of dipping/solid volume ratio is 1.8 with the solution impregnation of 180 milliliters of cobalt chloride, 0.33m% Platinic chloride and 1.67m%HCl that contain 0.67m%.110 ℃ of evaporate to dryness mother liquors, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 10 hours.Then in air, 510 ℃, water/cl molar ratio are activation treatment 6 hours under 30: 1 the condition, and 500 ℃ obtained mixture in 4 hours with hydrogen reducing.With 180 milliliters of this mixture concentration Hypophosporous Acid, 50 (hypophosphorous acid) solution that is 0.44m%, dipping is 1 hour under room temperature, nitrogen atmosphere, temperature is raised to 120 ℃ again, in 1 hour with excessive solution evaporate to dryness, under this temperature, keep carrying out in 6 hours drying, then in 523 ℃ with hydrogen reducing 4 hours, obtain catalyzer H, its composition sees Table 1.
Comparative Examples 3
The preparation active ingredient is the spherical catalyst of Pt, P.
Method according to example 1 prepares comparative catalyst K, and different is that (2) step carrier of dipping is an alumina supporter, contains the phosphoric acid of 0.53m% in the steeping fluid, and the composition of catalyzer K sees Table 1.
Example 6
This example is estimated activity of such catalysts of the present invention and selectivity.
On 10 micro-reactors, be that reaction raw materials is estimated catalyst A～E of the present invention and comparative catalyst F, H, K with 70～150 ℃ virgin naphthas.The raw material oil properties sees Table 2.Appreciation condition is: 0.70MPa, hydrogen/oil volume than 800: 1, during feed volume air speed 2.0
-1, the conditioned reaction temperature is 490 ℃, 500 ℃, 510 ℃, 520 ℃ respectively, records aromatics yield and liquid yield, it the results are shown in Figure 1, Fig. 2.
As seen from Figure 1, Figure 2, under the situation that identical virtue contains, the C of catalyst A～E
5 +Yield is all than the contrast medium height.Fig. 1 shows the increase with phosphorus content in the catalyzer, C
5 +Liquid is received the amplitude that increases and is increased.Illustrate that catalyzer of the present invention has higher selectivity than the comparative catalyst.
Table 1
Table 2
| Instance number | The catalyzer numbering | Catalyzer is formed, m% | ||||
| ????Pt | ????Sn | ????P | ????Cl | ????Co | ||
| ????1 | ????A | ????0.28 | ????0.30 | ????0.10 | ????1.12 | ????- |
| ????2 | ????B | ????0.28 | ????0.30 | ????0.30 | ????1.17 | ????- |
| ????3 | ????C | ????0.28 | ????0.30 | ????0.60 | ????1.05 | ????- |
| ????4 | ????D | ????0.28 | ????0.30 | ????0.30 | ????1.15 | ????- |
| ????5 | ????E | ????0.28 | ????0.30 | ????0.30 | ????1.18 | ????- |
| Comparative Examples 1 | ????F | ????0.28 | ????0.30 | ????- | ????1.20 | ????- |
| Comparative Examples 2 | ????H | ????0.28 | ????0.30 | ????0.30 | ????1.18 | ????1.00 |
| Comparative Examples 3 | ????K | ????0.28 | ????- | ????0.30 | ????1.10 | ????- |
| Density (20 ℃), Kg/m 3 | ????727.4 |
| ASTM D-86 boiling range, ℃ initial boiling point/50%/final boiling point | ????86/109/151 |
| Form m% alkane/naphthenic hydrocarbon/aromatic hydrocarbons | ????55.70/41.38/2.92 |
| Arene underwater content, % | ????41.59 |
Claims (12)
1, a kind of reforming catalyst comprises alumina supporter and active ingredient composed as follows, and described each active ingredient is all in element, and its content serves as to calculate benchmark with the butt aluminum oxide,
Platinum 0.01～2.0m%
Metal 0.01～the 5.0m% of IVA family
Phosphorus 0.01～10.0m%
Halogen 0.1～10.0m%
2,, it is characterized in that the content of described each active ingredient is according to the described catalyzer of claim 1:
Platinum 0.05～1.0m%
Metal 0.1～the 2.0m% of IVA family
Phosphorus 0.05～5.0m%
Halogen 0.1～3.0m%
3, according to claim 1 or 2 described catalyzer, it is characterized in that described IVA family metal is a tin, halogen is a chlorine.
4, according to the described catalyzer of claim 3, it is characterized in that the atomic ratio of phosphorus and platinum is 0.5～20: 1 in the catalyzer, the atomic ratio of phosphorus and tin is 0.2～15.0: 1, and alumina supporter is that the aluminium hydroxide by aluminum alkoxide hydrolysis by-product makes high-purity gama-alumina.
5, according to the described catalyzer of claim 4, it is characterized in that the atomic ratio of phosphorus and platinum is 1～10: 1 in the catalyzer, the atomic ratio of phosphorus and tin is 0.5～10.0: 1.
6, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) with aluminium hydrate powder making beating, acidifying, the solubility IVA family metallic compound that adds predetermined amount stirred 0.5～4.0 hour with the urea that accounts for aluminium hydrate powder weight 20～40%, adding accounts for the kerosene of aluminium hydrate powder weight 0 or 10～40% again, 2～6% fatty alcohol-polyoxyethylene ether stirred 0.5～4.0 hour, drip ball forming then, dry back obtains containing the carrier of IVA family metal in 370～600 ℃ of roastings
(2) with soaking altogether or the method for step impregnation is introduced platinum and phosphorus in the carrier that contains IVA family metal,
(3), in 315～650 ℃ of hydrogen, reduced 0.5～10.0 hour with after solid drying, the roasting behind the above-mentioned dipping.
7, in accordance with the method for claim 6, it is characterized in that used solubility IVA family metallic compound of (1) step is selected from tin protochloride, tin tetrachloride or stannic chloride pentahydrate.
8, in accordance with the method for claim 6, it is characterized in that described altogether leaching method is with containing the carrier that solution impregnation that platinic compound and P contained compound be made into contains IVA family metal, after the drying, in air in 370～700 ℃, H
2Handle 0.5～20.0 hour under the condition of O/HCl mol ratio 1.0～150: 1, and then use hydrogen reducing.
9, in accordance with the method for claim 6, it is characterized in that the described branch method of soaking is the carrier that contains earlier IVA family metal with the platiniferous solution impregnation, the P contained compound solution impregnation is used in drying, roasting again, after the drying, in air in 370～700 ℃, H
2Handle 0.5～20.0 hour under the condition of O/HCl mol ratio 1.0～150: 1, and then use hydrogen reducing.
10, according to claim 8 or 9 described methods, when it is characterized in that soaking platinum, adding HCl and trichoroacetic acid(TCA) are competitive adsorbate in steeping fluid, and the weight ratio of HCl and trichoroacetic acid(TCA) is 0.01～100: 1.
11, according to claim 8 or 9 described methods, it is characterized in that the described platinic compound that contains is selected from Platinic chloride, P contained compound is selected from phosphoric acid, triphenylphosphine, phosphorus trichloride or phosphorus tribromide.
12, in accordance with the method for claim 6, it is characterized in that described reduction temperature of (3) step is 400～600 ℃, the time is 0.5～5.0 hour.
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| CN100338189C (en) * | 2004-05-14 | 2007-09-19 | 中国石油化工股份有限公司 | Method for preparing reforming catalyst in platinum, stannum series |
| CN101294102B (en) * | 2007-04-28 | 2011-06-15 | 中国石油化工股份有限公司 | Petroleum naphtha reforming catalyst and preparation method thereof |
| CN101850997B (en) * | 2009-03-31 | 2012-07-18 | 中国石油化工股份有限公司 | Method for preparing spherical alumina |
| CN101940935B (en) * | 2009-07-09 | 2012-08-22 | 中国石油化工股份有限公司 | Bimetal reforming catalyst and preparation method thereof |
| CN102941109A (en) * | 2012-11-16 | 2013-02-27 | 浙江大学 | Silicon carbide foam-containing noble metal catalyst |
| CN103055930A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst and preparation method |
| CN103372454A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Multimetal reforming catalyst and preparation and applications thereof |
| CN104971742A (en) * | 2014-04-11 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Method of removing impurity iron from platinum-tin reforming catalyst |
| CN105561991A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Pt-Sn bimetal reforming catalyst and preparation method thereof |
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2002
- 2002-01-10 CN CNB021002266A patent/CN1191331C/en not_active Expired - Lifetime
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| CN100338189C (en) * | 2004-05-14 | 2007-09-19 | 中国石油化工股份有限公司 | Method for preparing reforming catalyst in platinum, stannum series |
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| CN101850997B (en) * | 2009-03-31 | 2012-07-18 | 中国石油化工股份有限公司 | Method for preparing spherical alumina |
| CN101940935B (en) * | 2009-07-09 | 2012-08-22 | 中国石油化工股份有限公司 | Bimetal reforming catalyst and preparation method thereof |
| CN103055930B (en) * | 2011-10-18 | 2015-03-18 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst and preparation method |
| CN103055930A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst and preparation method |
| CN103372454A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Multimetal reforming catalyst and preparation and applications thereof |
| CN103372454B (en) * | 2012-04-27 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of multimetal reforming catalyst and preparation and application thereof |
| CN102941109A (en) * | 2012-11-16 | 2013-02-27 | 浙江大学 | Silicon carbide foam-containing noble metal catalyst |
| CN104971742A (en) * | 2014-04-11 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Method of removing impurity iron from platinum-tin reforming catalyst |
| CN104971742B (en) * | 2014-04-11 | 2017-11-24 | 中国石化扬子石油化工有限公司 | The method for removing impurity iron in platinum tin reforming catalyst |
| CN105561991A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Pt-Sn bimetal reforming catalyst and preparation method thereof |
| CN105561991B (en) * | 2014-10-10 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of Pt-Sn dual metal reforming catalysts and preparation method |
| CN114620705A (en) * | 2022-02-24 | 2022-06-14 | 浙江诺亚氟化工有限公司 | Method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide |
| CN114620705B (en) * | 2022-02-24 | 2023-05-09 | 浙江诺亚氟化工有限公司 | Method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide |
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