CN105435821A - Three-metal reforming catalyst, preparation method and application - Google Patents
Three-metal reforming catalyst, preparation method and application Download PDFInfo
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Abstract
The invention provides a three-metal reforming catalyst, and a preparation method and application thereof. The catalyst comprises a carrier, and metal compositions and a halogen supported by the carrier, and the metal compositions comprise Pt, Pd and Re with the molar ratio of 1:(0.9-5):(1.1-2.1). The catalyst is low in platinum content, and the production cost of the catalyst is substantially reduced. Also, the catalyst possesses good catalytic activity, selectivity, activity stability and carbon-deposition resistance, and possesses extremely good industrial application prospect.
Description
Technical field
The present invention relates to a kind of three metal reforming catalysts, and a kind of preparation method of three metal reforming catalysts and the application of described three metal reforming catalysts in catalytic reforming, specifically, three metal reforming catalysts of the platiniferous palladium rhenium of a kind of load on carrier and its preparation method and application are related to.
Background technology
Catalytic reforming take naphtha cut as the significant process of raw material production high octane gasoline component and aromatic hydrocarbons, and the hydrogen of by-product is also as the main source facing hydrogen processing unit (plant) hydrogen simultaneously.Along with society constantly rises to the demand of reformate and hydrogen, people constantly improve reforming process and catalyst.
In recent years, the production capacity of world's catalytic reforming unit increases fast, and wherein, continuous reforming process technology is widely applied owing to can carry out large-scale production.Semi regeneration reforming process technology due to plant investment few, flexibly simple to operate, the advantage that producing cost is low, thus still in occupation of critical role.
From nineteen sixty-eight United States Patent (USP) 3,415,737 release Pt-Re catalyst, the eighties United States Patent (USP) 4,356, the reforming catalyst of 081 proposition Re content higher (Re/Pt is 2-3), its reactivity worth etc. is improved again.Thereafter, Pt-Re catalyst is always in occupation of the leading position of semi regeneration reforming catalyst.Although adding of rhenium constituent element can make the stability of catalyst significantly improve, too increase the hydrogenolysis activity of catalyst, cause the selective poor of Pt-Re catalyst.In order to improve the catalyst activity of bimetallic Pt-Re catalyst further, selective, reduce carbon deposition rate, people except improving in the kind, purity, pore structure, forming technique etc. of alumina support, mainly by introducing one or more metals or non-metal assistant in bimetallic Pt-Re catalyst, by these auxiliary agents to the inhibitory action of the hydrogenolysis activity of bimetallic constituent element or the inhibitory action to the generation of carbon distribution precursor, improve the anti-carbon performance of catalyst, and improve selective.
USP3,776,860 introduce one in rear earth element nd, praseodymium, samarium, ytterbium or two kinds in Pt-Re catalyst, and obtained catalyst choice and activity stability all increase; Reforming catalyst disclosed in CN1147536A contains platinum, rhenium, titanium, aluminium and halogen, though the activity and selectivity of this catalyst increases, lytic activity is still higher; Introduce a small amount of phosphorus constituent element in Pt-Re catalyst disclosed in CN1393513A, though the introducing of phosphorus can improve catalyst performance, activity stability still has much room for improvement.
As can be seen here, in current reforming catalyst, the main constituent element of metal active is all platinum constituent element without exception, and other metals or nonmetal constituent element are all auxiliary agent constituent elements platinum being carried out to modulation.But platinum is expensive metal, and test show, in Pt-Re catalyst, Pt content lower than 0.17 % by weight time, the catalytic performance of catalyst will obviously be deteriorated.And due to platinum content can not be too low, and the introducing of multiple high-purity promoter metal constituent element, catalyst manufacturing cost is increased again to some extent, and this just causes holding at high price of reforming catalyst.
Summary of the invention
The object of this invention is to provide one and can reduce platinum content, and there are three metal reforming catalysts of good catalytic activity, selective, activity stability and carbon accumulation resisting ability and its preparation method and application.
The present inventor finds in research process, in platinum-rhenium catalyst, introduce low-cost group VIII metal palladium, in the molar ratio range that Pt, Pd, Re are suitable, Pt-Pd-Re catalyst is compared with Pt-Re catalyst, and its catalytic activity, selective and activity stability all increase, simultaneously Pt content, Re content decreases, and shows that Metal Palladium plays the double action of active component and auxiliary agent in suitable molar ratio range thus.
According to aforementioned discovery, for realizing aforementioned object of the present invention, according to a first aspect of the invention, the invention provides a kind of three metal reforming catalysts, this catalyst comprises: metal component on carrier of carrier and load and halogen, wherein, described metal component comprises: Pt, Pd and Re, and the mol ratio of Pt, Pd and Re is 1:(0.9-5): (1.1-2.1).
According to a second aspect of the invention, the invention provides a kind of method preparing three metal reforming catalysts, wherein, the method comprises:
(1) by containing containing platinum compounds, containing palladium compound, containing the solution to be impregnated of rhenium compound and halogen contained compound and carrier and/or carrier Precursor exposure;
(2) rotation evaporate to dryness is carried out by contacting the mixture obtained;
Wherein, described containing platinum compounds, make with containing the consumption of rhenium compound containing palladium compound, in the catalyst prepared, the mol ratio of Pt, Pd and Re is 1:(0.9-5): (1.1-2.1).
According to a third aspect of the invention we, the invention provides a kind of three metal reforming catalysts obtained according to method of the present invention.
According to a forth aspect of the invention, the invention provides the application of three metal reforming catalysts of the present invention in catalytic reforming.
Catalyst platinum content of the present invention is low, greatly reduces the production cost of catalyst, and simultaneously catalyst of the present invention has good catalytic activity, selective, activity stability and carbon accumulation resisting ability.As can be seen here, catalyst of the present invention has good prospects for commercial application.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
As previously mentioned, the invention provides a kind of three metal reforming catalysts, this catalyst comprises: metal component on carrier of carrier and load and halogen, wherein, described metal component comprises: Pt, Pd and Re, and the mol ratio of Pt, Pd and Re is 1:(0.9-5): (1.1-2.1).
Catalyst according to the invention, preferably with the gross weight of catalyst for benchmark, the content of metal component is 0.15-4 % by weight, be preferably 0.3-0.95 % by weight, be more preferably 0.45-0.63 % by weight; The content of halogen is 0.1-3 % by weight, is preferably 1-1.6 % by weight.So can improve the catalytic activity of catalyst and selective etc. further.
Catalyst according to the invention, halogen is preferably chlorine.So can improve the catalytic activity of catalyst and selective etc. further.
Catalyst according to the invention, wherein, preferably with the gross weight of catalyst for benchmark, the content of Pt is 0.05-0.8 % by weight, be preferably 0.1-0.21 % by weight; The content of Pd is 0.05-1 % by weight, is preferably 0.1-0.35 % by weight; The content of Re is 0.1-1.6 % by weight, is preferably 0.1-0.32 % by weight; The content of halogen is 0.5-2 % by weight, is preferably 1-1.6 % by weight.So can improve the catalytic activity of catalyst and selective etc. further.
Catalyst according to the invention, the range of choices of described carrier is wider, and preferred described carrier is Al
2o
3, more preferably described carrier is γ-Al
2o
3, preferred γ-Al further
2o
3for the γ-Al adopting the obtained HP dry glue powder (α-mono-water boehmite) of low-carbon alkoxy aluminium hydrolysis or SB dry glue powder (import α-mono-water boehmite) to prepare for raw material
2o
3, be more preferably the γ-Al prepared for raw material with the HP dry glue powder that low-carbon alkoxy aluminium hydrolysis is obtained
2o
3.Wherein, HP dry glue powder, for adopting the preparation of domestic prior art, uses its preparation can reduce production cost further.
Catalyst according to the invention, described carrier can be one or more in spherical, bar shaped, cloverleaf pattern, butterfly, sheet and graininess, and preferred described carrier is bar shaped and/or spherical, and more preferably described carrier is cylinder bar shaped.So can improve the catalytic activity of catalyst and selective etc. further.
In the present invention, described carrier can be prepared according to a conventional method, such as, comprise the steps such as shaping, dry, pelletizing, roasting.
It is low that Above-mentioned catalytic agent of the present invention has platinum content, and there is good catalytic activity, selective, the advantage such as activity stability and carbon accumulation resisting ability, the present invention to the preparation method of Above-mentioned catalytic agent without particular/special requirement, as long as the catalyst with above-mentioned composition can be prepared, according to one of the present invention preferred embodiment, adopt and prepare Above-mentioned catalytic agent of the present invention with the following method and can improve catalytic activity, selective, activity stability and carbon accumulation resisting ability etc. further.
According to one of the present invention preferred embodiment, the invention provides a kind of method preparing three metal reforming catalysts, wherein, the method comprises: (1) is by containing containing platinum compounds, containing palladium compound, containing the solution to be impregnated of rhenium compound and halogen contained compound and carrier and/or carrier Precursor exposure; (2) rotation evaporate to dryness is carried out by contacting the mixture obtained; Wherein, described containing platinum compounds, make with containing the consumption of rhenium compound containing palladium compound, in the catalyst prepared, the mol ratio of Pt, Pd and Re is 1:(0.9-5): (1.1-2.1).
According to method of the present invention, in step (1), the method for contact can be room temperature immersion, the method of dipping can be saturated dipping or supersaturation dipping, be preferably supersaturation dipping, Gu the liquid/volume ratio of supersaturation dipping solution to be impregnated used and carrier and/or carrier predecessor is greater than 1.0; More preferably the liquid-solid volume ratio of described solution to be impregnated and carrier and/or carrier predecessor is (1-2): 1, is more preferably (1.1-1.2): 1.Wherein, liquid-solid ratio refers to the volume ratio of the liquor capacity of solution to be impregnated and the solid of carrier and/or carrier predecessor.
Described in further preferred steps (1), the condition of contact comprises: temperature is room temperature, is preferably 0-40 DEG C.
Described in further preferred steps (1), the condition of contact comprises the time is 1-10h, is preferably 4-6h.
According to method of the present invention, the condition rotating evaporate to dryness described in preferred steps (2) comprises: pressure is 0.01-0.05MPa, is more preferably 0.02-0.03MPa.
According to method of the present invention, the condition rotating evaporate to dryness described in preferred steps (2) also comprises: temperature is 20-90 DEG C, is more preferably 40-60 DEG C.
According to method of the present invention, the condition rotating evaporate to dryness described in preferred steps (2) also comprises: linear velocity is 0.02-0.08 meter per second, more preferably 0.02-0.05 meter per second.
According to method of the present invention, the range of choices of the described kind containing platinum compounds is wider, can be various water-soluble platinum salt (being such as platinum chloride, platinum nitrate etc.), platinic acid, be preferably in chloroplatinic acid, ammonium choroplatinate, dichlorodiamine base platinum, tri-chlorination platinum and platinum tetrachloride one or more, be preferably chloroplatinic acid and/or ammonium choroplatinate containing platinum compounds for the present invention.
According to method of the present invention, the range of choices of the described kind containing palladium compound is wider, can be various water-soluble containing palladium compound, be such as water-soluble palladium salt, for the present invention, be preferably in palladium bichloride, ammonum chloropalladate, dichloro diamino palladium, palladium and palladium nitrate one or more, more preferably palladium bichloride and/or dichloro diamino palladium.
According to method of the present invention, the range of choices of the described kind containing rhenium compound is wider, can be various water-soluble containing rhenium compound, be such as water-soluble rhenium salt, rehenic acid etc., be preferably in perrhenic acid, perrhenic acid amine and potassium perrhenate one or more, for the present invention, preferably containing rhenium compound is perrhenic acid.
According to method of the present invention, the range of choices of the kind of described halogen contained compound is wider, and be Cl for the preferred described halogen of the present invention, more preferably described halogen contained compound is HCl and/or trichloroacetic acid.
According to method of the present invention, preferred the method also comprises: the solid obtained after rotation evaporate to dryness is carried out drying, activation and reduction successively, wherein, drying, activation and reduction can be carried out according to the conventional method of this area, for the present invention, the condition of preferred drying comprises: temperature is 110-130 DEG C, and the more preferably dry time is 4-6h.
According to method of the present invention, the condition of preferably activation (also known as roasting) comprising: 400-600 DEG C in air stream, preferred 480-500 DEG C, activation 4-8 hour.
According to method of the present invention, the condition of preferably reduction comprises: 400-500 DEG C in hydrogen stream, is preferably 480-500 DEG C of reductase 12-4 hours, and the volume ratio 400-1200:1 of hydrogen and solid, be preferably 400-800:1.
The invention provides a kind of three metal reforming catalysts obtained according to method of the present invention.
The invention provides the application of three metal reforming catalysts of the present invention in catalytic reforming.
Catalyst of the present invention in the application, preferably changes catalyst vulcanization into sulphided state to make the activity component metal of catalyst by metal simple-substance state, to suppress catalyst at application initial stage too high hydrogenolysis activity.Wherein, sulfuration adds sulfur-containing compound (dimethyl disulfide or carbon disulfide etc.) in the hydrogen gas stream, make the gross mass relative to catalyst, sulfur content is 0.01-1 % by weight, be preferably 0.04-0.1 % by weight, wherein, curing temperature is preferably 370-450 DEG C, is more preferably 400-420 DEG C.In the present invention, the vulcanisation step of preferred catalyst is carried out when catalyst application.
Catalyst of the present invention is applicable to the catalytic reforming reaction of hydro carbons, and the preferred boiling range of reforming raw oil is the full cut straight-run naphtha of 40-230 DEG C or mixes the catalytic reforming reaction of boiling range 40-230 DEG C gasoline of the explained hereafter such as coking, cracking.
The reaction condition that catalyst of the present invention is suitable for preferably includes: pressure is 0.1-5.0MPa, is more preferably 0.3-2.5MPa; Feed volume air speed is 0.1-10hr
-1, more preferably 0.5-5.0hr
-1; Hydrogen/oil volume, than being 400-1600:1, is more preferably 500-1200:1; Inlet temperature is 370-600 DEG C, is more preferably 450-550 DEG C.
Further illustrate the present invention below by embodiment, but the present invention is not limited to this.
In the present invention, liquid is received and is referred to the mass fraction that product liquid (reformed oil) accounts for feedstock oil charging, calculates: quality × 100 of reformed oil quality/feedstock oil charging.
In the present invention, virtue accounts for the mass fraction of reformed oil containing referring to all aromatic hydrocarbons in reformed oil, calculates: quality × 100 of all aromatics quality/reformed oils in reformed oil.
In the present invention, conversion ratio refers to the mass fraction that aromatics yield accounts for feedstock oil arene underwater content.Calculate: aromatics yield/arene underwater content × 100.
In the present invention, octane number refers to the research octane number (RON) (RONC) producing the gasoline obtained, testing standard: GB/T5487-1955.
Carrier preparation example 1
This carrier preparation example 1 is for being that bar shaped γ-Al prepared by raw material with HP dry glue powder
2o
3carrier
Getting 500 grams of HP dry glue powders (production of Nanjing catalyst plant) is mixed even with 14 grams of field mountain valley with clumps of trees and bamboo dried bean noodles, with 360 milliliters of deionized waters, 12 ml concns are the nitric acid (AR level) of 68 % by weight, 14 ml concns are the acetic acid (AR level) of 32 % by weight, the mixed solution of 15 grams of citric acids (AR level), add wet mixing in the HP dry glue powder mixed with field mountain valley with clumps of trees and bamboo powder, roll, then the cylinder orifice plate extruded moulding in Φ 1.6mm aperture is used, in 30-60 DEG C of health 16 hours, drying 8 hours at 120 DEG C, pelletizing length is to 3-8mm, roasting 6 hours at 630 DEG C, obtain strip γ-Al
2o
3carrier (is called for short HP-γ-Al
2o
3).
Carrier preparation example 2
Carrier is prepared according to the method for carrier preparation example 1, unlike, the raw material of use is SB dry glue powder (German Condea company produces), prepares strip γ-Al
2o
3carrier (is called for short SB-γ-Al
2o
3).
Wherein, the analysis data of the alumina support of carrier preparation example 1 and carrier preparation example 2 are in table 1.
Catalyst preparation example 1
Concentration be the platinum acid chloride solution 13.4 milliliters of 0.0075 gram of Pt/ milliliter, solid palladium chloride 0.504 gram, concentration is perrhenic acid solution 12.2 milliliters, the 1:1 (HCl:H of 0.0165 gram of Re/ milliliter
2the volume ratio of O) 8.5 milliliters, the watery hydrochloric acid of concentration, deionized water 140 milliliters preparation solution to be impregnated in, drops into the γ-Al of 100 grams of embodiments 1 preparations
2o
3carrier (liquid-solid volume ratio is 1.2:1), room temperature 20 DEG C dipping is after 6 hours, send in rotary vacuum evaporator and carry out Rotary drying, controlled condition is: 0.02MPa, linear velocity 0.05 meter per second, 60 DEG C, then take out solid, by it 120 DEG C of dryings 4 hours, then in air atmosphere and air stream in 500 DEG C of roastings (namely activate) 4 hours, then at H
2in 480 DEG C of reductase 12s hour in atmosphere and hydrogen stream, wherein, the volume ratio 500:1 of hydrogen/solid, obtains reduction-state catalyst A of the present invention, and composition is in table 2.
Catalyst preparation example 2-5
According to the method Kaolinite Preparation of Catalyst of catalyst preparation example 1, unlike, with hydrochloric acid, the deionized water preparation maceration extract of the chloroplatinic acid of different scheduled volume, palladium bichloride, perrhenic acid and identical amount, prepare the catalyst B of the mol ratio of different Pt, Pd, Re content, C, D, E, composition is in table 2.
Catalyst preparation example 6
According to the method Kaolinite Preparation of Catalyst of catalyst preparation example 1, unlike, use the carrier S B-γ-Al that carrier preparation example 2 obtains
2o
3kaolinite Preparation of Catalyst F, composition is in table 2.
CATALYST PREPARATION Comparative's example 1
According to the method Kaolinite Preparation of Catalyst of catalyst preparation example 1, unlike, in preparation process, do not add palladium bichloride, preparation is not containing the reduction-state Pt-Re bimetallic catalyst D1 of palladium constituent element, and composition is in table 2.
Evaluation test example 1
On 100 milliliters of middle-scale devices of band hydrogen recycle compressor, the catalyst A prepared the present invention for feedstock oil with refining naphtha (character is in table 3), B, C, D, E, F and contrast medium D1 carry out catalytic reforming evaluation, the catalyst loaded, first at 420 DEG C, contains the H of 0.1 % by weight (relative to catalyst) in hydrogen stream
2vulcanizing treatment is carried out under the condition of S.
Wherein, catalytic reforming appreciation condition: 1.2MPa, feed volume air speed 2.0hr
-1, hydrogen/hydrocarbon volume ratio 1000:1, inlet temperature: 450 DEG C, 470 DEG C, 490 DEG C, evaluation result is in table 4.
From the data of table 4, catalyst of the present invention under each lower temperature conditions, conversion ratio and octane number all compared with the height of contrast medium D1, during identical octane number, liquid is received also higher than contrast medium D1, illustrates that catalyst of the present invention has higher catalytic activity and arenes selectivity.
Evaluation test example 2
On 100 milliliters of middle-scale devices of band hydrogen recycle compressor, the catalyst A prepared the present invention for feedstock oil with refining naphtha (character is in table 5) and contrast medium D1 carry out the acceleration carbon distribution evaluation under harsh conditions, the catalyst loaded, first at 420 DEG C, contains the H of 0.1 % by weight (relative to catalyst) in hydrogen stream
2vulcanizing treatment is carried out under the condition of S.
Accelerate carbon distribution appreciation condition: 0.69MPa, feed volume air speed 2.0hr
-1, hydrogen/hydrocarbon volume ratio 500:1, inlet temperature: 530 DEG C, accelerates to liquid and receives when being elevated to more than 95 % by weight, and terminate to evaluate, evaluation result is in table 6.
Table 1 aluminium oxide analysis result
Table 2 catalyst composition result
The feedstock oil composition of table 3 evaluation test example 1
The evaluation result of table 4 evaluation test example 1
The feedstock oil composition of table 5 evaluation test example 2
The acceleration carbon distribution evaluation result of table 6 evaluation test example 2
As shown in Table 6, under low pressure, low hydrogen/gasoline ratio (i.e. hydrogen/hydrocarbon volume ratio), hot conditions, the reforming activity of catalyst A of the present invention, be selectively all better than contrast medium D1, and the carbon accumulation resisting ability of catalyst A is strong, carbon deposition quantity is lower than the carbon deposition quantity of contrast medium D1 by 26.8%, and this shows that the activity of catalyst of the present invention and stability all have and greatly improves.And as can be seen from the result of table 6, catalyst of the present invention, carbon accumulation resisting ability, sulfur resistive ability are strong.
Catalyst preparation example 7
Preparation has the catalyst of same composition with the catalyst of catalyst preparation example 1, unlike, ammonium choroplatinate is used to replace chloroplatinic acid, dichloro diamino palladium to replace palladium bichloride, trichloroacetic acid replaces hydrochloric acid, and the liquid-solid volume ratio of immersive contact is 1.1:1, temperature is 0 DEG C, flood 4 hours, Rotary drying controlled condition is: 0.03MPa, linear velocity 0.02 meter per second, 40 DEG C, then take out solid, by it 110 DEG C of dryings 6 hours, then in air atmosphere and air stream in 480 DEG C of roastings (namely activate) 8 hours, then at H
2reduce 4 hours in 500 DEG C in atmosphere and hydrogen stream, wherein, the volume ratio 800:1 of hydrogen/solid, obtains reduction-state catalyst G of the present invention.
Catalyst preparation example 8
Preparation has the catalyst of same composition with the catalyst of catalyst preparation example 1, unlike, the liquid-solid volume ratio of immersive contact is 1.15:1, and temperature is 40 DEG C, floods 5 hours, Rotary drying controlled condition is: 0.025MPa, linear velocity 0.03 meter per second, 50 DEG C, then take out solid, by it 130 DEG C of dryings 5 hours, then in air atmosphere and air stream in 490 DEG C of roastings (namely activate) 6 hours, then at H
2reduce 4 hours in 490 DEG C in atmosphere and hydrogen stream, wherein, the volume ratio 400:1 of hydrogen/solid, obtains reduction-state catalyst H of the present invention.
Catalyst preparation example 9
Preparation has the catalyst of same composition with the catalyst of catalyst preparation example 1, unlike, platinum tetrachloride is used to replace chloroplatinic acid, palladium to replace palladium bichloride, potassium perrhenate replaces perrhenic acid, and the liquid-solid volume ratio of immersive contact is 1.05:1, and temperature is 60 DEG C, flood 2 hours, Rotary drying controlled condition is: 0.01MPa, linear velocity 0.08 meter per second, 80 DEG C, and other conditions are all identical, obtain reduction-state catalyst J of the present invention.
Evaluation test example 3
Evaluate according to the method for evaluation test example 1, evaluating inlet temperature is 450 DEG C, unlike, the catalyst of use is G, H, J, the results are shown in Table 7.
Table 7
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (10)
1. a metal reforming catalyst, this catalyst comprises: metal component on carrier of carrier and load and halogen, it is characterized in that, described metal component comprises: Pt, Pd and Re, and the mol ratio of Pt, Pd and Re is 1:(0.9-5): (1.1-2.1).
2. catalyst according to claim 1, wherein, with the gross weight of catalyst for benchmark, the content of metal component is 0.15-4 % by weight, and the content of halogen is 0.1-3 % by weight, and halogen is preferably chlorine.
3. catalyst according to claim 1 and 2, wherein, with the gross weight of catalyst for benchmark, the content of Pt is 0.05-0.8 % by weight, is preferably 0.1-0.21 % by weight;
The content of Pd is 0.05-1 % by weight, is preferably 0.1-0.35 % by weight;
The content of Re is 0.1-1.6 % by weight, is preferably 0.1-0.32 % by weight;
The content of halogen is 0.5-2 % by weight, is preferably 1-1.6 % by weight.
4. catalyst according to claim 1 and 2, wherein, described carrier is γ-Al
2o
3, the HP dry glue powder preferably adopting low-carbon alkoxy aluminium hydrolysis obtained or SB dry glue powder are γ-Al prepared by raw material
2o
3, be more preferably the γ-Al prepared for raw material with the HP dry glue powder that low-carbon alkoxy aluminium hydrolysis is obtained
2o
3, described carrier is one or more in spherical, bar shaped, cloverleaf pattern, butterfly, sheet and graininess, and preferred described carrier is bar shaped and/or spherical, and more preferably described carrier is cylinder bar shaped.
5. prepare a method for three metal reforming catalysts, it is characterized in that, the method comprises:
(1) by containing containing platinum compounds, containing palladium compound, containing the solution to be impregnated of rhenium compound and halogen contained compound and carrier and/or carrier Precursor exposure;
(2) rotation evaporate to dryness is carried out by contacting the mixture obtained;
Wherein, described containing platinum compounds, make with containing the consumption of rhenium compound containing palladium compound, in the catalyst prepared, the mol ratio of Pt, Pd and Re is 1:(0.9-5): (1.1-2.1).
6. method according to claim 5, wherein,
Described in step (1), the condition of contact comprises: temperature is 0-40 DEG C, and the time is 1-10h; The liquid-solid ratio of described solution to be impregnated and carrier and/or carrier predecessor is greater than 1, is preferably (1.1-1.2): 1;
The condition rotating evaporate to dryness described in step (2) comprises: pressure is 0.01-0.05MPa, is preferably 0.02-0.03MPa; Temperature is 20-90 DEG C, is preferably 40-60 DEG C; Linear velocity is 0.02-0.08 meter per second, preferred 0.02-0.05 meter per second.
7. the method according to claim 5 or 6, wherein, be one or more in chloroplatinic acid, ammonium choroplatinate, dichlorodiamine base platinum, tri-chlorination platinum and platinum tetrachloride containing platinum compounds, be one or more in palladium bichloride, ammonum chloropalladate, dichloro diamino palladium, palladium and palladium nitrate containing palladium compound, be one or more in perrhenic acid, perrhenic acid amine and potassium perrhenate containing rhenium compound, halogen contained compound is HCl and/or trichloroacetic acid.
8. the method according to claim 5 or 6, wherein, the method also comprises: the solid obtained after rotation evaporate to dryness is carried out drying, activation and reduction successively, wherein,
Dry condition comprises: temperature is 110-130 DEG C, and the time is 4-6h;
The condition of activation comprises: 400-600 DEG C of activation 4-8 hour in air stream;
The condition of reduction comprises: 400-500 DEG C of reductase 12-4 hours in hydrogen stream, and the volume ratio 400-1200:1 of hydrogen and solid.
9. three metal reforming catalysts that the method in a claim 5-8 described in any one obtains.
10. the application of three metal reforming catalysts in catalytic reforming that the method in three metal reforming catalysts in a claim 1-4 described in any one and claim 5-8 described in any one obtains.
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