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CN1047326C - Platinum-rhenium reforming catalyst - Google Patents

Platinum-rhenium reforming catalyst Download PDF

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CN1047326C
CN1047326C CN95106352A CN95106352A CN1047326C CN 1047326 C CN1047326 C CN 1047326C CN 95106352 A CN95106352 A CN 95106352A CN 95106352 A CN95106352 A CN 95106352A CN 1047326 C CN1047326 C CN 1047326C
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catalyzer
carrier
catalyst
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CN1137943A (en
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孙作霖
史佩芬
谷婉华
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Sinopec Research Institute of Petroleum Processing
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Abstract

The present invention relates to a Pt and Re reforming catalyst. A carrier is formed by the proportional mixture of GM single diaspore which is prepared by an aluminum sol hot oil ageing method and Ziegler synthesis auxiliary SB single diaspore. Composite gamma-Al2O3 with two concentrated hole peaks is prepared by forming and roasting. The catalyst comprises 0.10 to 1.00 wt% of Pt, 0.10 to 3.00 wt% of Re, 0.00 to 0.20 wt% of Sn, and 0.50 to 3.00 wt% of Cl. The catalyst has the characteristics of high activity, high selectivity and low carbon deposit. The catalyst of the present invention can be applied to a reforming process for virgin naphtha with the distillation range of 40 to 230 DEG or gasoline which is produced by coking, cracking, etc. in the processing of the virgin naphtha by mixing with petroleum.

Description

A kind of platinum-rhenium reforming catalyst
The invention belongs to catalyst for reforming naphtha, specifically contain the catalyzer that is used for petroleum naphtha bimetal or multimetal reforming of platinum, rhenium precious metal constituent element.
The petroleum naphtha catalytic reforming is the important means that improves gasoline octane rating and obtain aromatic hydrocarbons, and platinum-rhenium reforming catalyst is widely used in the reformation full scale plant owing to its activity stability is good.In recent years, the demand of stop bracket gasoline and aromatic hydrocarbons constantly increases, and therefore needs exploitation under the high severity operational condition, the reforming catalyst of use properties excellence.
The reforming catalyst of excellent property not only needs the metal constituent element of good hydrogenation-dehydrogenation functionality but also the carrier that needs one have suitable isomerization acid function.That reforming catalyst is the most frequently used is γ-Al 2O 3And η-Al 2O 3
The alumina preparation method difference, there is very big difference in its performance, and then the performance of catalyzer is had bigger influence.Some documents have been introduced the aluminum oxide that uses the different methods preparation and have been done carrier to improve the performance of catalyzer: as using the mixture of Al2O3 and ZSM-5 molecular sieve as the preparing carriers reforming catalyst among the USP4276151; USP4407736 and USP4298461 propose to use Al 2O 3And SiO 2Make the reforming catalyst carrier; Use Pt/ γ-Al among the USP4263134 2O 3With Ir/ η-Al 2O 3The dual metal reforming catalyst that mixes; USP3280041 is the preparing carriers reforming catalyst with the SB aluminum oxide of Ziegler building-up reactions by-product.Recently to adopt the HP aluminum oxide that the low-carbon alkoxy aluminium hydrolysis makes or sneak into part therein be the preparing carriers catalyzer with single diaspore of additive method preparation to CN1032951A, obtained activity and selectivity preferably.CN1055192A is the aluminium hydroxide with the different methods preparation, the γ-Al that makes after high-temperature water atmosphere acidification 2O 3As the reforming catalyst carrier, improved activity of such catalysts, selectivity and stability, in a word, platinum-rhenium reforming catalyst of the prior art compares with the reforming catalyst of other classes, and active and stability improves a lot, but selectivity still has the leeway of raising.
The object of the present invention is to provide a kind of catalyst for reforming naphtha that is applicable to the good high rhenium platinum of low pressure reforming process, reactivity worth than (Re/Pt is 2~4).
Catalyzer provided by the invention has following composition (with the butt aluminum oxide is benchmark, heavy %): Pt0.10~1.00 are preferably 0.10~0.60; Re0.10~3.00 are preferably 0.10~2.00; Sn0.00~0.20 is preferably 0.00~0.11; Cl0.50~3.00 are preferably 0.80~2.00; Surplus is compound γ-Al 2O 3Carrier.This compound γ-Al 2O 3Precursor be the single diaspore of GM and the mixture of the single diaspore of the synthetic by-product SB of Ziegler that aluminium colloidal sol deep fat ageing process is produced according to 5: 1~1: 5 weight ratio composition, its optimum weight ratio is 3: 1~1: 3.This catalyzer rhenium platinum weight ratio is 0.1~4.0, is preferably 1.0~3.0.
Used compound γ-Al among the present invention 2O 3The preparation method be: the single diaspore of the GM that aluminium colloidal sol is made is worn into granularity and is mixed by a certain percentage with the SB powder less than 200 purpose powderies, through an extrusion molding or a ball forming, 60~80 ℃ of dryings 4~12 hours, 120~130 ℃ of dryings 6~24 hours, vapour agent volume ratio is 400~700 in the presence of dry air then), through 450~700 ℃ of best 550~650 ℃ of roastings, get final product compound γ-Al 2O 3Carrier.
Catalyst preparation process provided by the present invention is promptly: the metal-salt of predetermined amount (to the platinum constituent element, is preferably Platinic chloride, ammonium chloroplatinate; The rhenium constituent element is preferably perrhenic acid, ammonium perrhenate, rhenium carbonyl), trichoroacetic acid(TCA) and/or hydrochloric acid, decationized Y sieve water mixed solution, under room temperature normal pressure or decompression, flood γ-Al 2O 3Complex carrier, the volume ratio of carrier and solution is 1.0~2.0, soak time is 6~24 hours, after the filtration, difference is dry 6~12 hours, 12~24 hours under 60~80 ℃, 110~130 ℃, activate 2~12 hours under 220 ℃, 450~550 ℃ respectively in the dry air, use hydrogen reducing 2~12 hours down at 400~500 ℃.
This catalyzer also can adopt step impregnation method, but must soak another component again after a kind of component on every dipping after super-dry, roasting.
Sn constituent element in the catalyzer can be introduced with coprecipitation method in the GM production process, and also available pickling process is introduced in the complex carrier.
The another kind of constituent element of catalyzer of the present invention is the halogen that comprises fluorine, chlorine, and is best with chlorine.Chlorine can be introduced in catalyst preparation process, also can in the catalyzer use, introduce, best mode be the form of or Organohalogen compounds inorganic with hydrochloric acid or other when dipping and the metal constituent element together introduce.
Catalyzer of the present invention can drip method moulding such as ball, spin granulation, compressing tablet, extruding with common.The gained respective shapes is sphere, particulate state, sheet shape or bar shaped (comprising abnormity such as cylindrical, trilobal, quatrefoil), is the most frequently used with sphere or bar shaped.
Catalyzer of the present invention is the same with other platinum-rhenium reforming catalysts must to pass through prevulcanized before use.Prevulcanized can be by injecting H in the hydrogen stream 2The mode of S or other organic or inorganic sulfide is carried out, and the sulphur content on the catalyzer is 0.01~2.00, and heavy % is preferably 0.04~0.15, heavy %.
The boiling range that catalyzer of the present invention can be used for explained hereafter such as the coking, cracking in virgin naphtha that boiling range is 40~230 ℃ (pressing the GB255 methods analyst, as follows) or its blending refining of petroleum is the reformation of 40~230 ℃ gasoline.
The present invention is because single diaspore of employing SB and the single diaspore of GM are mixed into feedstock production γ-Al by a certain percentage 2O 3Carrier, the compound γ-Al that makes 2O 3Two concentrated Kong Feng are arranged, and acidity obtains modulation, with this compound γ-Al 2O 3The catalyzer of preparing carriers has following characteristics: active high, under same reaction conditions, composite carried catalyst is than the fragrant product of single carrier (GM) catalyzer high 0.8~2.0 heavy %; Selectivity is good, when the liquid product aromaticity content is identical, and liquid product yield high 1.1~3.2 heavy %; Good stability, catalyzer metal particle diameter after thermal sintering is little, is 1.9~3.2 nanometers; Under identical life cycle, coke deposit rate is low.
Example 1
This case introduction compound γ-Al provided by the invention 2O 3The preparation method of carrier.
Coccoid preparing carriers method:
The GM that aluminium colloidal sol deep fat ageing process is made by elder generation 1(not containing the Sn constituent element) single diaspore (Fushun No.3 Petroleum Factory, technical grade) is worn into less than 200 purpose fine powders, by 1: 1 mixed, adds an amount of decationized Y sieve water with the single diaspore of SB (German condea company) then, at room temperature stirs 0.5 hour, makes its pulp.The single diaspore of per then 100 grams adds 5.5~5.7 milliliters of rare nitric acid (analytical pure, HNO 3: H 2O=1: 1), acidifying 3 hours, the slurries after the acidifying drip ball forming in oil-ammonia becomes goalpost, use the decationized Y sieve water washing then three times, 60 ℃~120 ℃ dryings 10~20 hours, dried bead promptly got coccoid compound γ-Al 580 ℃ of blowing air roastings 4 hours 2O 3Carrier, note is made compound SG1.
The GM that aluminium colloidal sol deep fat ageing process is made 2(contain the Sn constituent element, its content is 0.22 heavy %) single diaspore (Fushun No.3 Petroleum Factory, technical grade) is worn into less than 200 purpose fine powders, mixes by 1: 1 with the single diaspore of SB then and makes coccoid compound γ-Al as stated above 2O 3Carrier, note is made compound SG 2
For the purpose of contrast, with single S B, GM 1, GM 2Single diaspore is made coccoid γ-Al by above-mentioned preparation method respectively 2O 3Carrier, and note is made list-SB, list-GM successively 1, list-GM 2
The strip carrier preparation method:
The single diaspore of GM that aluminium colloidal sol deep fat ageing process is made is worn into less than 200 purpose fine powders, mix by 1: 1 with the single diaspore of SB, add to mix behind an amount of decationized Y sieve water, peptizing agent and the extrusion aid and pinch, extruded moulding then, drying again, 650 ℃ of roastings are 4 hours in water vapour atmosphere, promptly get the compound γ-Al of strip 2O 3Carrier, note is made compound SG bar.
For the purpose of contrast, the single diaspore of single S B, GM is made strip γ-Al by above-mentioned preparation method 2O 3, note is made list-SB bar and list-GM bar respectively.
Table 1 and table 2 have been listed coccoid respectively and physical and chemical performance strip carrier, and intensity is wherein measured with ZQJ intelligence granule strength trier, and specific surface, pore volume, pore radius distribute and measure with static nitrogen loading capacity method.
Find out from table 1, table 2: the intensity of complex carrier, specific surface is all suitable with the single carrier of SB, GM, bulk density is between SB and the single carrier of GM, but pore volume increases than SB carrier, and pore distribution is changed into the double hole channel structure of 30~50 and two concentrated honeybees of 50~100 by the single separately concentrated peak of 50~100 of 30~50 , the GM of SB.
Example 2
This case introduction is with compound γ-Al 2O 3The method of preparing carriers catalyzer.
Platinic chloride, perrhenic acid, hydrochloric acid and the trichoroacetic acid(TCA) of preparation are mixed, make to contain the heavy % of Pt0.11 in the mixed solution the heavy % of Re0.33, the heavy % of HCl1.0, CCl 3The heavy % of COOH5.0 is (with Al 2O 3Be benchmark), (0.067~0.093MPa) dipping composite S G under room temperature, decompression 1Carrier, liquid-solid volume ratio are 1.4, flood 24 hours after-filtration, and 60 ℃, 120 ℃ were descended dry 6 and 12 hours respectively, activated 4 hours under 220 ℃, 500 ℃ respectively then in air, hydrogen reducing 4 hours, and in hydrogen stream, inject H 2The S sulfuration, H 2Till S adds to beds and penetrates, promptly get catalyst A-1.
A-2, A-3 support of the catalyst and the same A-1 of preparation method, just Pt, Re content difference.
The B-3 support of the catalyst is composite S G 2, the same A-1 of method for preparing catalyst, but Pt, Re content difference.
C-1, C-2, C-3 support of the catalyst are single S B, the same basically A-1 of Preparation of catalysts method, and different is Pt, Re content, liquid-solid volume ratio is 1.2.
D-1, D-2, D-3 support of the catalyst are single GM 1, preparation method and A-1 are basic identical, and different is Pt, Re content, and liquid-solid volume ratio is 1.7.
The E-3 support of the catalyst is single GM 2, the same basically A-1 of preparation method, different is Pt, Re content, liquid-solid volume ratio is 1.7.
The G support of the catalyst is composite S G 1, the same basically A-1 of preparation method, but Pt, Re content difference.
The H support of the catalyst is composite S G 1, the same basically A-1 of preparation method, but Pt, Re content difference, HCl consumption 0.8 heavy % during dipping, CCl 3The heavy % of COOH6.0.
The F-1 support of the catalyst is a composite S G bar, the same basically A-1 of method for preparing catalyst, and different is Pt, Re content, CCl during dipping 3The COOH consumption is 6.0 heavy %, and liquid-solid volume ratio is 1.6.
The F-2 support of the catalyst is a list-SB bar, the same basically A-1 of method for preparing catalyst, and different is Pt, Re content, and the amount of HCl is 0.8 heavy % during dipping, and liquid-solid volume ratio is 1.3.
The composition of spherical catalyzer and strip catalyst sees Table 3 and table 4 respectively, Pt wherein, Re, Sn content X-ray fluorescence spectrometry, and the Re/Pt weight ratio calculates according to analytical results.
Example 3
The thermostability of this example explanation catalyzer of the present invention.
For the purpose of contrast, the catalyzer that catalyzer that single carrier is made and complex carrier are made carries out sintering thermal treatment, and treatment condition are H 2Atmosphere was handled 8 hours for following 700 ℃, gas agent ratio is 700/1, handle rear catalyst and test its grain size with JEM2000Fx-II Electronic Speculum, the results are shown in Table 5, catalyzer CB-6, CB-7 are platinum-rhenium catalysts that Changling Refining Plant of Chinese General Petrochemical Industrial Cooperation produces in the table 5, E-603, E803 are U.S. Engelhard company product, and G, H catalyzer are to use composite S G 1Be carrier, the catalyzer of prepared in laboratory.
As seen from Table 5: catalyzer after heat treatment, the Pt-Re median size is different, by catalyzer G, the H metal particle diameter minimum of complex carrier preparation, thereby has excellent thermostability, shows that complex carrier changes to some extent with respect to the performance of single carrier.
Example 4
The reactivity worth of catalyzer when this example illustrates different Pt content.
On the pressurization micro-reactor, be that A-1, C-1, D-1 and the Pt content of 0.1 heavy % is that A-2, the C-2 of 0.2 heavy %, the reactivity worth of D-2 catalyzer (the Re/Pt ratio is 3) are estimated to Pt content respectively.Little anti-condition of pressurizeing:
Raw material: normal heptane catalyzer Intake Quantity: 0.7150 gram
Pressure: 0.98MPa air speed (weight): 5.7 o'clock -1
Hydrogen-oil ratio (body): 1200: 1 temperature: 500 ℃
The pressurization micro anti-evaluation the results are shown in table 6
The little converse result of table 6 shows: when the heavy % of Pt content 0.1, i.e. and A-1, C-1, D-1 catalyzer complex carrier SG 1Catalyzer (A-1) transformation efficiency is the highest, and aromatization activity is best.When Pt content is 0.2 heavy %, i.e. A-2, C-2, D-2 catalyzer, complex carrier SG 1The more single GM of catalyzer (A-2) transformation efficiency 1The carried catalyst height, aromatization activity is suitable; The more single SB carrier of liquid yield height illustrates that the more single carried catalyst of its combined reaction performance is good.
Example 5
Catalytic perfomance when containing Sn and not containing Sn in this example explanation support of the catalyst.
Be that 0.18 heavy %, Re/Pt weight ratio are that 4 A-3, B-3 (containing Sn), C-3, D-3, E-3 (containing Sn) catalyzer carry out the reactivity worth evaluation to Pt content on the pressurization micro-reactor, little anti-condition of pressurizeing is with example 4, and evaluation result is listed in table 7.
The evaluation result of table 7 shows: do not contain under the situation of Sn complex carrier SG in carrier 1Catalyzer (A-3) and single GM 1It is suitable that carried catalyst (D-3) is compared reactivity worth, but better than single SB carried catalyst (C-3) aromatization activity and selectivity.In carrier, contain under the situation of Sn composite carried catalyst (B-3) transformation efficiency and active apparently higher than single GM 2Carried catalyst (E-3).
Example 6
The reactivity worth of this example explanation strip catalyst.
On the pressurization micro-reactor, extruded moulding catalyzer F-1, F-2 are carried out the reactivity worth evaluation, catalyzer Re/Pt weight ratio is 2, and little anti-condition of pressurizeing is with example 4, and evaluation result is listed in table 8.
Table 8 evaluation result shows: composite S G bar is made the catalyzer of carrier and is compared with the catalyzer that list-SB bar is done carrier, and the former weighs % than the latter low 1.38 by aromatization activity, but liquid yield is than the latter high 2.66 heavy %.Thereby with the selectivity of catalyst of strip complex carrier preparation single-SB bar to make the catalyzer of carrier good.
Example 7
This example is to activity of such catalysts of the present invention and optionally evaluation on 100 milliliters of middle-scale devices.
Catalyst A-4 that this example is used and the composition of comparative catalyst D-4 and carrier form and physical and chemical performance is listed in the table 9.The preparation method of A-4 and D-4 is basically respectively with A-1 and D-1.
A-4 and comparative catalyst D-4 are estimated on 100 milliliters of middle-scale devices of band hydrogen gas compressor, raw materials used oil is mixing 60~155 ℃ of straight-run spirit of grand celebration Renqiu, its hydrocarbon composition sees Table 10, appreciation condition: pressure 1.47MPa, during volume space velocity 2.0-1, hydrogen to oil volume ratio 1000/1, estimate general data and list in table 11, the result shows: catalyst A of the present invention-4 is compared with comparative catalyst D-4, under 490 ℃~500 ℃, aromatics yield high 0.8~2.0 heavy %, when aromaticity content is identical in the liquid product, liquid product yield high 1.1~3.2 heavy %.
Example 8
This example is an activity of such catalysts stability experiment of the present invention.
The composition of catalyst system therefor A-5 and comparative catalyst C-4 and the physical and chemical performance of carrier thereof see Table 12.This two Preparation of catalysts method is basically with A-1 in the example 1 and C-1, and used evaluating apparatus is identical with example 7 with stock oil.Appreciation condition: when the active stage pressure 1.47MPa of initial activity and recovery, volume space velocity 2.0 -1, hydrogen to oil volume ratio 1000/1.Accelerate 540 ℃ of aging step temperature, when pressure 0.69MPa, volume space velocity 3.0 -1, hydrogen to oil volume ratio 400/1.Evaluation result sees Table 13.
Table 13 shows that the initial activity of catalyst A of the present invention-5 is suitable with comparative catalyst C-4, but stability is better than C-4, and average carbon deposit rate obviously reduces.Use bar shaped catalyst also can obtain similar results.
The method of calculation of average carbon deposit rate are in the table
Table 1
Bearer number List-SB List-GM 1 List-GM 2 Composite S G 1 Composite S G 2
Bulk density, grams per milliliter 0.82 0.62 0.59 0.78 0.82
Intensity, newton/grain 67.6 71.5 71.5 66.6 72.5
Specific surface, rice 2/ gram 195 195 215 195 210
Pore volume, milliliter/gram 0.48 0.65 0.71 0.61 0.52
Pore radius distributes, body % 30-50 93.65 12.02 14.60 62.60 33.97
50-100 2.89 72.68 72.15 35.64 52.44
100-200 3.46 8.19 10.60 1.76 10.59
200-300 -- 3.22 2.60 -- 2.99
>300 -- 3.89 -- -- --
Table 2
Bearer number List-SB bar List-GM bar Composite S G bar
Bulk density, grams per milliliter 0.76 0.65 0.72
Intensity, newton/grain 128 69 87
Specific surface, rice 2/ gram 221 152 195
Pore volume, milliliter/gram 0.49 0.57 0.58
Pore radius distributes, body % <30 11.10 1.82 0.18
30-50 72.61 14.30 70.71
50-100 1.84 82.46 22.98
100-300 14.45 1.27 6.12
Table 3
Carrier The catalyzer numbering Catalyzer is formed, heavy % Re/Pt is heavy
Pt Re Sn
Composite S G 1 A-1 0.12 0.39 -- 3.25
SB C-1 0.11 0.31 -- 2.82
GM 1 D-1 0.11 0.35 -- 3.18
Composite S G 1 A-2 0.21 0.62 -- 2.95
SB C-2 0.22 0.59 -- 2.68
GM 1 D-2 0.22 0.61 -- 2.77
Composite S G 1 A-3 0.16 0.69 -- 4.31
Composite S G 2 B-3 0.18 0.70 0.11 3.89
SB C-3 0.18 0.69 -- 3.83
GM 1 D-3 0.18 0.72 -- 4.00
GM 2 E-3 0.18 0.69 0.22 3.83
Composite S G 1 G 0.19 0.65 -- 3.42
Composite S G 1 H 0.20 0.63 -- 3.15
Table 4
Bearer number The catalyzer numbering Catalyzer is formed, heavy % Re/Pt is heavy
Pt Re Sn
Composite S G bar F-1 0.21 0.42 -- 2.0
List-SB bar F-2 0.20 0.44 -- 2.2
Table 5
The catalyzer numbering Carrier Catalyzer is formed, heavy % Pt-Re median size after the thermal sintering, nanometer
Pt Re
CB-6 SB 0.29 0.27 4.8
CB-7 SB 0.21 0.42 5.1
E-603 0.29 0.30 22.1
E-803 0.22 0.45 23.7
G Composite S G 1 0.19 0.65 3.2
H Composite S G 1 0.20 0.63 1.9
Table 6
The catalyzer numbering Carrier Evaluation result, heavy %
Transformation efficiency C 1~C 5 Benzene and toluene Liquid yield
A-1 SG 1 88.56 36.08 20.37 63.92
C-1 SB 85.56 34.21 16.76 65.79
D-1 GM 1 72.12 26.68 8.47 73.32
A-2 SG 1 90.46 41.82 18.30 58.18
C-2 SB 91.33 45.25 20.27 54.75
D-2 GM 1 88.95 39.76 18.50 60.24
Table 7
The catalyzer numbering Carrier Evaluation result, heavy %
Transformation efficiency C 1~C 5 Benzene and toluene Liquid yield
A-3 SG 1 88.93 42.79 16.67 57.21
B-3 SG 2 87.92 41.41 14.12 58.59
C-3 SB 88.10 43.65 14.71 56.35
D-3 GM 1 88.80 42.31 16.33 57.69
E-3 GM 2 81.10 30.43 11.08 69.57
Table 8
The catalyzer numbering Bearer number Evaluation result, heavy %
Transformation efficiency C 1~C 5 Benzene and toluene Liquid yield
F-1 Composite S G bar 90.20 42.35 19.78 57.65
F-2 List-SB bar 91.49 45.01 21.16 54.99
Table 9
The catalyzer numbering A-4 D-4
Carrier is formed carrier character bulk density, grams per milliliter intensity, newton/grain specific surface, rice 2/ gram pore volume, milliliter/gram can several apertures, the pore radius distributes, body % 30-50, 50-100, 100-200, 200-300, 75%SB 25%GM 1 0.73 81.3 220 0.57 43 86.22 12.97 0.81 -- 100%GM 1 0.55 63.7 195 0.69 98 9.13 59.38 27.65 3.84
Catalyzer is formed, heavy % Pt Re Cl Re/Pt is heavy 0.20 0.64 1.19 3.20 0.23 0.61 1.05 2.65
Table 10
The stock oil hydrocarbon composition, heavy %
Alkane Naphthenic hydrocarbon Aromatic hydrocarbons Virtue is dived
53.47 39.93 6.60 43.15
Table 11
Figure C9510635200181
Table 12
The catalyzer numbering A-5 C-4
Carrier is formed carrier character bulk density, grams per milliliter intensity, newton/grain specific surface, rice 2/ gram pore volume, milliliter/gram can several apertures, the pore radius distributes, body %<30, 30-50, 50-100, 100-200, 50%SB 50%GM 1 0.71 63.7 195 0.56 52 -- 57.15 42.15 0.70 100%SB 0.82 86.2 211 0.50 38 1.12 90.92 1.72 6.23
Catalyzer is formed, heavy % Pt Re Cl Re/Pt is heavy 0.19 0.52 1.06 2.74 0.20 0.51 1.25 2.55
Table 13
Figure C9510635200201

Claims (8)

1, a kind of catalyst for reforming naphtha has following composition (with the butt aluminum oxide is benchmark, heavy %):
Pt 0.10~1.00
Re 0.10~3.00
Sn 0.00~0.20
Cl 0.50~3.00
And the compound γ-Al of surplus 2O 3Carrier;
Described compound γ-Al 2O 3Precursor be single diaspore of producing of aluminium colloidal sol deep fat ageing process and the mixture of single diaspore of the synthetic by-product of Ziegler according to 5: 1~1: 5 weight ratio composition.
2,, it is characterized in that this catalyzer has following composition (with the butt aluminum oxide is benchmark, heavy %) according to the described catalyzer of claim 1
Pt 0.10~0.60
Re 0.10~2.00
Sn 0.00~0.11
Cl 0.80~2.00
And the compound γ-Al of surplus 2O 3Carrier;
Described compound γ-Al 2O 3Precursor be single diaspore of producing of aluminium colloidal sol deep fat ageing process and the mixture of single diaspore of the synthetic by-product of Ziegler according to 3: 1~1: 3 weight ratio composition.
3,, it is characterized in that catalyzer Re/Pt weight ratio is 0.1~4.0 according to claim 1 or 2 described catalyzer.
4,, it is characterized in that catalyzer Re/Pt weight ratio is 1.0~3.0 according to the described catalyzer of claim 3.
5, according to claim 1 or 2 described catalyzer, it is characterized in that compound γ-Al 2O 3Carrier be mixture by its precursor through moulding, make 450~700 ℃ of following roastings.
6, according to the described catalyzer of claim 5, it is characterized in that compound γ-Al 2O 3The maturing temperature of carrier is 550~650 ℃.
7, according to claim 1 or 2 described catalyzer, it is characterized in that the Sn constituent element can be with the coprecipitation method introducing in single diaspore production process that aluminium colloidal sol deep fat ageing process is produced, also available pickling process is introduced in the complex carrier.
8,, it is characterized in that it is that the boiling range of coking, cracking explained hereafter in 40~230 ℃ virgin naphtha or its blending refining of petroleum is 40~230 ℃ a gasoline that described petroleum naphtha is selected from boiling range according to claim 1 or 2 described catalyzer.
CN95106352A 1995-06-14 1995-06-14 Platinum-rhenium reforming catalyst Expired - Fee Related CN1047326C (en)

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CN102139222B (en) * 2010-01-29 2012-12-12 中国石油化工股份有限公司 Platinum rhenium reforming catalyst and preparation method thereof

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CN104841425A (en) * 2014-02-18 2015-08-19 中国石油化工股份有限公司 Semi-regenerated catalytic reforming catalyst and preparation method thereof
CN108236964A (en) * 2016-12-27 2018-07-03 中国石油天然气股份有限公司 Bimetallic catalytic reforming catalyst containing L T L type molecular sieve

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