CN102139222A - Platinum rhenium reforming catalyst and preparation method thereof - Google Patents
Platinum rhenium reforming catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a platinum rhenium reforming catalyst, comprising a carrier and the following active components by taking the carrier as reference: 0.01-2.0wt% of platinum family metal, 0.05-2.0wt% of VIIB family metal, 0.1-5.0wt% of halogen and 0.1-0.3wt% of sulphate radical, wherein the sulphate radical is uniformly distributed in the catalyst. The sulphate radical is introduced in the preparation process of the catalyst, the obtained catalyst can be contacted with reformer feed oil for reforming reaction without presulphurization, the catalyst has the advantages of longer service life and better catalytic performance, and the operating step is simplified.
Description
Technical field
The present invention is a kind of dual metal reforming catalyst and preparation method thereof, specifically, is a kind of platinum-rhenium reforming catalyst and preparation method thereof.
Background technology
Catalytic reforming is important oil refining process, octane number or the lower naphtha of arene content can be changed into the product of high-knock rating gasoline or high arene content, the hydrogen of the cheapness of production high-quality simultaneously.Catalytic reforming process mainly is divided into continuous reforming process and half generative reforming technology, and it is that initial activity and selectivity are good under the low pressure that continuous reforming catalyst uses platinum-tin catalyst, characteristics, but less stable needs cyclic regeneration to keep the performance of catalyst.Catalyst does not need to carry out presulfurization before use after overactivation, reduction.Half generative reforming catalyst uses platinum-rhenium catalyst, and characteristics are good stabilities, and selectivity is poor slightly, can the long period steady running, and the regeneration period can reach 2～3 years.Catalyst needs to carry out presulfurization before use after overactivation, reduction handles.
Half generative reforming catalyst develops into platinum-rhenium catalyst from single platinum catalyst, and the stability of catalyst obviously improves, and coke deposit rate obviously reduces, and obviously prolong service cycle.The introducing of rhenium makes the active obviously raising of catalyst hydrogenolysis, and the selection of catalysts reduction must be by the hydrogenolysis activity of presulfurization catalyst deactivation.After the platinum-rhenium catalyst presulfurization, the stability of catalyst is further enhanced.At present, platinum-rhenium catalyst is carried out presulfurization two kinds of methods: a kind of is under certain temperature, pressure, introduces certain amount of H in hydrogen
2S carries out presulfurization to catalyst lentamente; Another kind is at certain temperature, pressure and faces under the condition of hydrogen be injected with machine sulfide in feedstock oil, as dimethyl disulfide, dimethyl sulfide etc.Utilize organic sulfur compound to decompose the H that generates
2S carries out presulfurization to catalyst.First method generally is used for laboratory research, and second method generally is used for the platinum-rhenium catalyst commercial plant and goes into operation.The essence of this dual mode all is to use H
2S carries out presulfurization to catalyst, all belongs to the gas phase sulfuration.
Hayes etc. (J Catal.1975,37:553～554) find that above-mentioned presulfurization can obviously reduce PtAl
2O
3The coke deposit rate of reforming catalyst, the cycle lie of prolongation catalyst.Ramaswamy (Proc.Inc.Congr.Catal.6
Th, 1976,2:1061～1070) though think that the dehydrogenation activity at metal active center, reforming catalyst sulfuration back descends, very stable; Though unvulcanized catalyst initial activity is very high, since excessively dehydrogenation, the rapid carbon deposit of catalyst, and deactivation rate is fast, poor stability.
CA748409A carries out presulfurization to the reforming catalyst gas with sulfur-bearing before oil-feed that contains Pt, presulfurization is carried out under the sulfiding gas of low sulfur content and high linear gas flow rate, sulfide is contacted with catalyst equably, and sulfur content is 0.01～0.03% in the catalyst.The sulfur-containing compound of the sulfide that presulfurization is used under conditions of vulcanization, decomposing, as hydrogen sulfide, disulphide or carbon disulfide etc., this presulfurization can be used for fresh dose, also can be used for regenerated catalyst, though the catalyst sulfur content after the presulfurization is low, but still contain same sulfur content, but obviously reduce without the coke content of the regenerated catalyst of presulfurization.
CA1125211, USP4220520 disclose the Al of a kind of Ir of containing
2O
3The method that reforming catalyst goes into operation, described catalyst also can comprise platinum, and this catalyst all need carry out presulfurization before use.Presulfurization is with containing a certain amount of H
2The hydrogen of S is handled catalyst, purges catalyst with pure hydrogen gas again, removes wherein unnecessary sulphur, and the activity and the stability of sulfuration rear catalyst all are improved.
USP4191633 discloses a kind of hydrogenolysis and C of suppressing in reformer
5 +The method of product liquid loss, this method is in the catalyst through at least five regeneration and activation, and only feeding contains the sulfide of 0.01% sulphur at the most, and then injects the water of 0.5～50ppm in raw material, the sulphur that adsorbs in the desorption catalyzing agent makes sulfur content in the gas reach the level of presulfurization requirement.
For the sulfate radical in the reforming catalyst, it is generally acknowledged the performance that can damage catalyst, be a kind of poisonous substance to catalyst.Hair [petroleum journal (petrochemical industry) such as learn military affairs, 2000 the 16th 2 phases of volume, P25-32] find that the formation of sulfate radical on the platinum-rhenium reforming catalyst has not only suppressed the acid function and the metal function of catalyst, accelerated the deactivation rate of catalyst simultaneously, aromatization activity and selectivity are declined to a great extent.
CN98117895.2 discloses the removal methods of sulfate radical on a kind of reforming catalyst, it is removed to the organochlorine compound that under this condition, decomposites hydrogen chloride because of the feeding of sulfate radical fouled catalyst bed at 400～600 ℃, this method is upgraded regeneration than the catalyst chlorination of routine, can effectively remove the sulfate radical in the catalyst.
[petroleum journal (petrochemical industry) such as Sun Fengduo, 1988 the 4th 1 phases of volume, P39-45] studied the influence of sulfate sulfur to platinum rhenium titanium reforming catalyst reactivity worth, use the agent treatment platinum rhenium titanium catalyst of three kinds of sulfur-bearing acid groups, make it contain the sulfate sulfur of 0.1m%, by investigating its dehydrogenation reaction result, think that its performance is approaching to hydrocarbon compound.It with the aluminum sulfate solution again the catalyst that maceration extract has prepared a series of different sulfate sulfur content, investigate its influence to each key reaction thing reaction result of reformer feed, think that an amount of sulfate sulfur (about 0.1m%) has reduced the initial activity of catalyst, but main is to have suppressed side reaction, thereby has improved the aromatisation selectivity of catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of platinum-rhenium reforming catalyst and preparation method thereof, this catalyst contains the sulfate radical of introducing in right amount in preparation process, and the preparation method simplifies, and the catalyst of preparation gets final product directly without presulfurization and feedstock oil reacts.
Platinum-rhenium reforming catalyst provided by the invention comprises carrier and is the following active component of content that benchmark calculates with the carrier:
Platinum group metal 0.01～2.0 quality %
VIIB family metal 0.05～2.0 quality %
Halogen 0.1～5.0 quality %
Sulfate radical 0.1～0.3 quality %
Described sulfate radical evenly distributes in catalyst.
Catalyst of the present invention is introduced an amount of sulfate radical in preparation process, and sulfate radical evenly distributes in catalyst, and this catalyst is used for naphtha reforming and does not need presulfurization, has simplified the catalyst preliminary treatment and the step that goes into operation, and catalyzer coke content reduces, and performance increases.
The specific embodiment
The present invention adopts the method for introducing sulfate radical in the process of dipping active component that platinum-rhenium reforming catalyst is carried out passivation, reduces its hydrogenolysis activity, improves selection of catalysts and stability.Being evenly distributed of sulfate radical in the catalyst of preparation do not need conventional presulfurization to handle before use, both simplified the catalyst structure step, simplified the step that goes into operation again, and the coke content of catalyst is descended to some extent.
The sulfate radical that catalyst of the present invention contains is evenly distributed, and the content difference of described sulfate radical at each position of catalyst is not more than 0.02 quality %.Preferred 0.12～0.25 quality % of the content of sulfate radical in the catalyst.
The preferred aluminium oxide of described catalyst carrier, the preferred platinum in the platinum group metal in the catalyst, the preferred rhenium of VIIB family metal, the preferred chlorine of halogen.
The shape of catalyst of the present invention can be ball-type, stripe shape, sheet, graininess or trifolium-shaped, preferred stripe shape or ball-type.
The mode that sulfate radical in the catalyst of the present invention can be taked to soak is altogether introduced carrier, and also the mode that can take branch to soak is introduced carrier, adopts when dividing the mode of soaking to introduce sulfate radical, and in the end a step is introduced carrier to sulfate radical.The carrier of introducing before the sulfate radical is not answered roasting, otherwise when introducing sulfate radical its distribution in carrier with inhomogeneous.
The present invention adopts common dipping to prepare the method for catalyst, comprises the maceration extract dipping of carrier with platinum group metallic element, VIIB family metallic element and sulfate radical, will flood back solid drying, roasting then.
The present invention adopts the branch dipping to prepare the method for catalyst, comprises the maceration extract dipping of carrier with platinum group metallic element and VIIB family metallic element, uses the solution impregnation of sulfur-bearing acid group after the drying again, dry then, roasting.
The inventive method preferably adopts dipping introducing active component in the rotation vacuum evaporation normal direction carrier, promptly with the state impregnated carrier of the maceration extract of preparing in rotation, rotation status preferably obtains in rotary vacuum evaporator, and then the solvent in the evaporation under reduced pressure maceration extract make the dipping solid be drying regime, solid is taken out further dry roasting from rotary evaporator.
Particularly, adopt the rotation vacuum vapor deposition method to flood the method for preparing catalyst altogether, comprise carrier maceration extract dipping with platinum group metallic element, VIIB family metallic element and sulfate radical under rotation status, continue dipping and evaporating solvent down in 0.01～0.08MPa pressure again, dry then, roasting.
Adopt rotation vacuum vapor deposition method step impregnation to prepare the method for catalyst, comprise carrier maceration extract dipping with platinum group metallic element and VIIB family metallic element under rotation status, continue dipping and evaporating solvent down in 0.01～0.08MPa pressure again, after drying, solution with the sulfur-bearing acid group is maceration extract rotary dipping and evaporating solvent as stated above, dry then, roasting.
In the above-mentioned dipping method, the liquid of maceration extract and carrier/solid volume is than greater than 1.0, and is preferred 1.05～2.0, and dipping temperature is 15～40 ℃, preferred 20～30 ℃, dip time preferred 1～8 hour, more preferably 2～4 hours.
In the said method, the preferred platinum of the platinum group in the maceration extract of preparation, the preferred rhenium of VIIB family metallic element.Platinum group in the maceration extract is preferably provided by chloroplatinic acid, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride dichloro carbonyl platinum, dinitro diaminourea platinum or tetranitro sodium platinate, VIIB family metallic element is preferably provided by perrhenic acid, ammonium perrhenate or potassium perrhenate, and sulfate radical is preferably provided by ammonium sulfate, sulfuric acid, aluminum sulfate or titanium sulfate.
The introducing of halogen component and the metal component even distribution on whole carrier for the benefit of, the general competitive adsorbate that adds in the dipping solution.Preferred competitive adsorbate is HCl or trichloroacetic acid, both can add maceration extract respectively, also can add maceration extract simultaneously, the weight ratio of HCl and trichloroacetic acid is 0.01～100: 1 in the maceration extract, preferred 0.1～10: 1, the concentration of competitive adsorbate in maceration extract is counted 0.2～5.0 quality % with chlorine, preferred 0.8～3.0 quality %.If adding trichloroacetic acid is competitive adsorbate, after the carrier drying, be preferably in 180～230 ℃ of heating 0.5～10 hour, in the maceration extract so that trichloroacetic acid desorption from carrier.
In the above-mentioned method for preparing catalyst, described baking temperature is 60～150 ℃, preferred 400～600 ℃ of sintering temperature.Roasting is carried out in air stream, and gas/agent volume ratio is preferably 500～1000: 1, and the time is preferably 4～8 hours.
Catalyst provided by the invention only need reduce before use, and need not carry out the presulfurization processing can direct and crude oil haptoreaction.Reduction is carried out in hydrogen atmosphere, preferred 400～500 ℃ of temperature, and gas/agent volume ratio preferred 500～1400: 1, the recovery time is preferably 4～8 hours.
Catalyst of the present invention is suitable for catalytic reforming reaction.Reformer feed is the whole-distillate gasoline of 40～230 ℃ of boiling ranges, the mixture of forming as the gasoline of straight run and cracking gasoline or its admixture heat cracking or catalytic cracking, part reformed naphtha or dehydrogenation naphtha.The reaction condition that catalyst of the present invention is suitable for is: 0.1～10.0MPa, preferred 0.3～2.5MPa, 370～600 ℃, preferred 450～550 ℃, hydrogen/hydrocarbon mol ratio 1～20, preferred 2～10, charging mass space velocity 0.1～20.0 hour
-1, preferred 0.5～5.0 hour
-1
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1～5
Prepare catalyst of the present invention.
Get the industrial bar shaped gamma-aluminium oxide carrier that the Chang Ling catalyst plant is produced, chloroplatinic acid, perrhenic acid, ammonium sulfate and hydrochloric acid are made into maceration extract, make the platinum that contains 0.22 quality % in the maceration extract, the rhenium of 0.46 quality %, the chlorine of 1.8 quality % and the sulfate radical (all with respect to the butt aluminium oxide) of scheduled volume, liquid/solid volume ratio is 1.3.Adopt rotation vacuum vapor deposition method impregnated carrier to introduce active component.Earlier carrier is placed rotary vacuum evaporator, keep 0.5h in the reduced pressure atmosphere of 0.02MPa, introduce maceration extract, pressure returns to 0.1MPa, carrier is under the rotation status at 30 ℃ floods 3h, under rotation status, continue dipping and solvent evaporated at 60 ℃, 0.02MPa subsequently.The catalyst that will be drying regime takes out further dry, is roasting 4 hours under 700 the condition in 500 ℃, gas/agent volume ratio in dry air, uses H again under 480 ℃, gas/agent volume ratio are 500 condition
2Reduced 4 hours, and made catalyst G～K, the content of sulfate radical and catalyst are formed and to be seen Table 1 in the used maceration extract of each example, and the catalyst granules sample of preparation is cutd open into 10 parts of samples, and the sulfate radical content in every part sees Table 2.
Example 6～7
Method by example 1 prepares catalyst, replace ammonium sulfate with sulfuric acid or aluminum sulfate when different is the preparation maceration extract, the predetermined content of sulfate radical is 0.18 quality % in the maceration extract, the composition that makes catalyst M and N sees Table 1 respectively, the catalyst granules sample cuts open into 10 parts of samples, and the sulfate radical content in every part sees Table 2.
Example 8
Prepare catalyst of the present invention.
Get the industrial bar shaped gamma-aluminium oxide carrier that the Chang Ling catalyst plant is produced, chloroplatinic acid, perrhenic acid, hydrochloric acid are made into maceration extract, wherein contain the platinum of 0.22 quality %, the rhenium of 0.46 quality % and the chlorine (all with respect to the butt aluminium oxide) of 1.8 quality %, liquid/solid volume ratio is 1.3.Earlier carrier is placed rotary vacuum evaporator, keep 0.5h in the reduced pressure atmosphere of 0.02MPa, introduce maceration extract, pressure returns to 0.1MPa, carrier is under the rotation status at 30 ℃ floods 3h, continue dipping and solvent evaporated at 60 ℃, 0.02MPa in rotation status subsequently.The catalyst that will be drying regime takes out further drying, and preparing ammonium sulfate subsequently is maceration extract, makes the sulfate radical that wherein contains 0.18 quality %, is rotated dipping and solvent evaporated as stated above.The catalyst that will be drying regime takes out further dry, is roasting 4 hours under 700 the condition in 500 ℃, gas/agent volume ratio in dry air, uses H again under 480 ℃, gas/agent volume ratio are 500 condition
2Reduced 4 hours, and made catalyst O, its composition sees Table 1, and the catalyst granules sample is cutd open into 10 parts of samples, and the sulfate radical content in every part sees Table 2.
Example 9
Get the industrial bar shaped gamma-aluminium oxide carrier that the Chang Ling catalyst plant is produced, chloroplatinic acid, perrhenic acid, ammonium sulfate and hydrochloric acid are made into maceration extract, liquid/solid volume ratio is 1.6, contains the chlorine (all with respect to the butt alumina support) of 0.22 quality %Pt, 0.46 quality %Re, 0.18 quality % sulfate radical, 1.8 quality % in the maceration extract.At 30 ℃ with maceration extract impregnated carrier 24 hours, remove by filter and soak surplus liquid, the gained solid is respectively at 60 ℃, 120 ℃ dry 12h, is roasting 4 hours under 700 the condition in 500 ℃, gas/agent volume ratio in dry air then, uses H again under 480 ℃, gas/agent volume ratio are 500 condition
2Reduced 4 hours, and made catalyst F, its composition sees Table 1, and the catalyst granules sample is cutd open into 10 parts of samples, and the sulfate radical content in every part sees Table 2.
Comparative Examples 1～3
Get the industrial oxidation state CB-70 catalyst 100g that the Chang Ling catalyst plant is produced, solution with ammonium sulfate, sulfuric acid, aluminum sulfate configuration is that maceration extract flooded 24 hours at 25 ℃ respectively, contain the sulfate radical (butt aluminium oxide relatively) of 0.18 quality % in the maceration extract, liquid during dipping/solid volume ratio is 1.6.To flood back gained solid 120 ℃ of dryings 12 hours, be roasting 4 hours under 700 the condition in 500 ℃, gas/agent volume ratio in the dry air, uses H again under 480 ℃, gas/agent volume ratio are 500 condition
2Reduced 4 hours, and made catalyst A, B, C, its composition sees Table 1, and various catalyst granules samples are cutd open into 10 parts of samples, and the sulfate radical content in every part sees Table 2.
Comparative Examples 4
Getting the industrial oxidation state CB-70 catalyst 100g that the Chang Ling catalyst plant is produced, is maceration extract with ammonium sulfate, makes the sulfate radical (butt aluminium oxide relatively) that wherein contains 0.18 quality %, and liquid/solid volume ratio is 1.3.Adopt the method impregnated carrier of example 1 described rotation vacuum evaporation to introduce sulfate radical, subsequently catalyst is carried out drying, roasting and reduction and make catalyst D, its composition sees Table 1, and the catalyst granules sample is cutd open into 10 parts of samples, and the sulfate radical content in every part sees Table 2.
Comparative Examples 5
Get the industrial bar shaped gamma-aluminium oxide carrier that the Chang Ling catalyst plant is produced, chloroplatinic acid, perrhenic acid, hydrochloric acid are made into maceration extract, liquid/solid volume ratio is 1.3.Carrier is placed rotary vacuum evaporator, keep 0.5h in the reduced pressure atmosphere of 0.02MPa, introduce maceration extract, pressure returns to 0.1MPa, carrier is under the rotation status at 30 ℃ floods 3h, continue dipping and solvent evaporated at 60 ℃, 0.02MPa in rotation status subsequently.The catalyst that will be drying regime takes out further dry, is roasting 4 hours under 700 the condition in 500 ℃, gas/agent volume ratio in dry air then, uses H again under 480 ℃, gas/agent volume ratio are 500 condition
2Reduced 4 hours, the hydrogen sulfide that adds 0.10% (with respect to catalyst quality) in 425 ℃, hydrogen stream carries out presulfurization to catalyst, makes catalyst E, and its composition sees Table 1.
Comparative Examples 6
Method by example 1 prepares catalyst, during different is preparation maceration extract in the maceration extract predetermined content of sulfate radical be 0.42 quality %, the composition that makes catalyst L sees Table 1, the catalyst granules sample cuts open into 10 parts of samples, the sulfate radical content in every part sees Table 2.
By table 2 data as can be known, catalyst of the present invention is than comparative catalyst A～D, sulfate radical wherein has distribution more uniformly, same catalyst granules cuts open into 10 samples, the sulfate radical content difference of each sample is no more than 0.02 quality %, and the sulfate radical content difference of 10 samples that comparative catalyst A～D particle cuts open is bigger.By table 1, table 2 data as can be known, with the catalyst F of the present invention that soaks the filtration method preparation altogether, than with rotation vacuum evaporation catalyst prepared I, though the sulfate radical content difference of 10 samples is less, the amount that goes up of sulfate radical differs bigger than scheduled volume.
Example 10
Catalyst performance is carried out micro anti-evaluation.
On 1mL micro anti-evaluation device, make raw material with normal heptane catalyst performance is estimated, appreciation condition: 500 ℃ of reactor inlet temperatures, reaction pressure 1.0MPa, mass space velocity 3.0h
-1, hydrogen/hydrocarbon volume ratio 1200: 1, the results are shown in Table 3.
Example 11
Catalyst performance is carried out medium-sized evaluation.
On the 100mL device, be that raw material is investigated catalyst and comparative catalyst's coke content of the present invention's preparation with refining naphtha, the results are shown in Table 4.Appreciation condition is: reaction pressure 0.69MPa, charging air speed 2.0h
-1, 520 ℃ of hydrogen/hydrocarbon volume ratio 700/1, reaction temperature.
Table 1
Table 2
Table 3
| The catalyst numbering | C 1～C 4, quality % | Benzene+toluene, quality % |
| G | 40.1 | ?34.6 |
| H | 38.0 | ?34.7 |
| I | 31.3 | ?33.9 |
| J | 31.3 | ?29.2 |
| K | 31.2 | ?28.0 |
| M | 30.9 | ?33.6 |
| N | 31.6 | ?33.7 |
| O | 31.0 | ?33.6 |
| F | 35.8 | ?24.6 |
| A | 36.5 | ?26.8 |
| B | 36.3 | ?26.6 |
| C | 36.2 | ?28.5 |
| D | 36.3 | ?27.7 |
| L | 30.8 | ?27.1 |
| E | 33.7 | ?30.7 |
Table 4
| The catalyst numbering | Coke content is than the increase and decrease amplitude of a reference value |
| G | -3％ |
| H | -7％ |
| I | -15％ |
| J | -12％ |
| K | -10％ |
| M | -14.7％ |
| N | -14.6％ |
| O | -14.8％ |
| F | +12％ |
| A | +6％ |
| B | +8％ |
| C | +5％ |
| D | +3.8％ |
| L | +4％ |
| E | 5.28 quality % |
As can be seen from Table 3, be benchmark with the comparative catalyst E that needs presulfurization, the C of comparative catalyst A, B, C, D
1～C
4Productive rate increases more than the 2 quality %, and (benzene+toluene) productive rate descends more than the 2 quality %, and these selection of catalysts decline is described, aromatization activity also descends.The C of catalyst F
1～C
4Productive rate increases more than the 2 quality %, and (benzene+toluene) productive rate descends more than the 6 quality %, and selection of catalysts decline is described, aromatization activity obviously descends, mainly due to quantity not sufficient on the sulfate radical.(benzene+toluene) productive rate of catalyst G, H all increases more than the 3 quality %, and the activity of this explanation catalyst aromatisation is improved; The C of catalyst I, M, N, O
1～C
4Productive rate descends more than the 2 quality %, and (benzene+toluene) productive rate increases about 3 quality %, illustrates that catalyst selectivity and aromatization activity all are improved; The C of catalyst J, K
1～C
4Productive rate descends more than the 2 quality %, illustrates that catalyst selectivity is improved.The selectivity of catalyst L increases, and aromatization activity descends.
As shown in Table 4, with comparative catalyst E is benchmark, the coke content of catalyst A, B, C all increases more than 5%, catalyst D, L carbon deposition quantity increase more than 3%, catalyst G～K, the M of the present invention's preparation, N, O coke content all descend to some extent, descend about 3～15% respectively, just the catalyst F coke content of immersion filtration method preparation increases.The coke content of catalyst reduces, and the stability of catalyst improves.
Claims (11)
1. platinum-rhenium reforming catalyst comprises carrier and is the following active component of content that benchmark calculates with the carrier:
Platinum group metal 0.01～2.0 quality %
VIIB family metal 0.05～2.0 quality %
Halogen 0.1～5.0 quality %
Sulfate radical 0.1～0.3 quality %
Described sulfate radical evenly distributes in catalyst.
2. according to the described catalyst of claim 1, it is characterized in that the content difference of described sulfate radical at each position of catalyst is not more than 0.02 quality %.
3. according to claim 1 or 2 described catalyst, the content that it is characterized in that sulfate radical in the described catalyst is 0.12～0.25 quality %.
4. according to claim 1 or 2 described catalyst, it is characterized in that described carrier is an aluminium oxide.
5. according to claim 1 or 2 described catalyst, it is characterized in that described platinum group metal is a platinum, VIIB family metal is a rhenium, and halogen is a chlorine.
6. the described Preparation of catalysts method of claim 1 comprises the maceration extract dipping of carrier with platinum group metallic element, VIIB family metallic element and sulfate radical, will flood back solid drying, roasting then.
7. in accordance with the method for claim 6, it is characterized in that carrier maceration extract dipping with platinum group metallic element, VIIB family metallic element and sulfate radical under rotation status, continue dipping and evaporating solvent down in 0.01～0.08MPa pressure again, dry then, roasting.
8. the described Preparation of catalysts method of claim 1 comprises the maceration extract dipping of carrier with platinum group metallic element and VIIB family metallic element, uses the solution impregnation of sulfur-bearing acid group after the drying again, dry then, roasting.
9. in accordance with the method for claim 8, it is characterized in that carrier maceration extract dipping with platinum group metallic element and VIIB family metallic element under rotation status, continue dipping and evaporating solvent down in 0.01～0.08MPa pressure again, after drying, solution with the sulfur-bearing acid group is maceration extract rotary dipping and evaporating solvent as stated above, dry then, roasting.
10. according to claim 6 or 8 described methods, it is characterized in that the platinum group in the maceration extract is a platinum, VIIB family metallic element is a rhenium.
11. according to claim 6 or 8 described methods, it is characterized in that the platinum group in the maceration extract is provided by chloroplatinic acid, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride dichloro carbonyl platinum, dinitro diaminourea platinum or tetranitro sodium platinate, VIIB family metallic element is provided by perrhenic acid, ammonium perrhenate or potassium perrhenate, and sulfate radical is provided by ammonium sulfate, sulfuric acid, aluminum sulfate or titanium sulfate.
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| CN105642319A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Vulcanized platinum-rhenium reforming catalyst and preparation method thereof |
| CN115999596A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon by dehydrogenation of six-membered cycloalkane and preparation method thereof |
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| US4220520A (en) * | 1978-11-16 | 1980-09-02 | Exxon Research & Engineering Co. | Startup method for a reforming process |
| US4966879A (en) * | 1989-07-03 | 1990-10-30 | Exxon Research & Engineering Company | Novel platinum-iridium reforming catalysts |
| CN1047326C (en) * | 1995-06-14 | 1999-12-15 | 中国石油化工总公司石油化工科学研究院 | Platinum-rhenium reforming catalyst |
| CN1191121C (en) * | 2001-05-30 | 2005-03-02 | 中国石油化工股份有限公司 | Reforming Pt-Re catalyst and its prepn |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105642319A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Vulcanized platinum-rhenium reforming catalyst and preparation method thereof |
| CN105642319B (en) * | 2014-12-04 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of vulcanization type platinum-rhenium reforming catalyst and preparation method thereof |
| CN115999596A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon by dehydrogenation of six-membered cycloalkane and preparation method thereof |
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| CN102139222B (en) | 2012-12-12 |
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