CN104841425A - Semi-regenerated catalytic reforming catalyst and preparation method thereof - Google Patents
Semi-regenerated catalytic reforming catalyst and preparation method thereof Download PDFInfo
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Abstract
A semi-regenerated catalytic reforming catalyst comprises, based on the content of dry basis alumina, 0.01-3.0mass% of a phosphorus-containing alumina carrier (by P), 0.01-2.0mass% of VIII group metal, 0.01-3.0mass% of VIIB group metal, 0.01-3.0mass% of IIIA group metal, 0.1-3.0mass% of halogen and 0.05-1.0mass% of sulfur. The catalyst has the advantages of high activity, high aromatic hydrocarbon selectivity and catalyst regeneration performance.
Description
Technical field
The present invention is a kind of catalyst for reforming naphtha and preparation method, specifically, is a kind of semi regeneration reforming catalyst and preparation method.
Background technology
Catalytic reforming be with cuts such as straight-run naphtha, hydrogenation coking naphtha, hydrocracked naphtha for the significant process of high-octane rating blended gasoline component and aromatic hydrocarbons produced by raw material, go back the cheap hydrogen that by-product refinery hydrogenation plant needs simultaneously.In recent years, constantly rise along with to the demand of Reformed Gasoline and aromatic hydrocarbons, the production capacity of world's catalytic reforming unit increases year by year, according to the report of U.S.'s gas magazine in 2011, although continuous reforming process technology in Asian-Pacific area development fast, but semi regenerative reformer still occupies critical role (working ability accounts for 54.4%), fixed bed circulation and regeneration technology also also has certain market (working ability accounts for 10.7%) abroad.Operation that fixed bed circular regeneration type technique under low pressure (can be less than 1.5MPa), can obtain high C
5 +reformed oil productive rate and hydrogen yield, can use the charging of wide boiling range, and can (mol ratio is less than 5.0) operation under low hydrogen/hydrocarbon ratio.Operation cycle becomes with feedstock property and product requirement, has good activity and selectivity with the catalyst in keeping system, and use interval time of each reactor is not from less than 1 week to 1 month etc.
At present, the catalyst of the industrial semi regeneration that generally adopts and fixed bed circulation and regeneration technology mostly is platinum rhenium catalyst series, though adding of rhenium component can make the stability of catalyst greatly increase, but too increase the hydrogenolysis activity of catalyst, cause the liquid product yield of catalyst and hydrogen purity lower, namely platinum-rhenium catalyst is selective poor, and this is disadvantageous to production high-knock rating gasoline.For the reformer producing aromatic hydrocarbons, wish that aromatics yield maximizes, the severity therefore produced is higher, in order to maintain the production cycle, needs exploitation coke deposit rate lower, the catalyst of good stability.
The total development trend of catalytic reforming process is to the future development to favorable thermodynamics, namely reduces reaction pressure, improves reaction temperature, requires again the reforming reaction liquid product yield that improves simultaneously and extends service cycle, to obtain better economic benefit.For many years, the development of domestic and international semi regeneration formula and fixed bed circular regeneration reforming catalyst be all improve the activity of catalyst, selective and stability is main target.
The common method improving above-mentioned reforming catalyst performance introduces one or more auxiliary agents, by these auxiliary agents to the inhibitory action of platinum rhenium metal component hydrogenolysis activity or the coking resistivity inhibitory action that carbon deposit precursor generates being improved to catalyst, and improve selective.
USP4483767, USP4463104 can improve the performance of catalyst after describing and introduce phosphorus on single platinum catalyst.USP4426279 discloses the preparation method of the reforming catalyst of a kind of platiniferous and phosphorus, containing the platinum of 0.01 ~ 5.0 heavy %, the phosphorus of 0.01 ~ 5.0 heavy % and 0.01 ~ 5.0 heavy chlorine of % and the alumina support of surplus in catalyst disclosed in this patent.Its improvements are impregnation sequences of active component, namely first introduce platinum in the carrier, and then introduce phosphorus constituent element.Catalyst obtained like this than introducing platinum and phosphorus in the carrier simultaneously, or first introduces phosphorus, and the catalyst that the method for rear introducing platinum obtains has higher C
5 +productive rate and more hydrogen output.
CN02100225.8 introduces a small amount of phosphorus to improve the selective of catalyst and coking resistivity in dual metal reforming catalyst.Containing the P elements of 0.1 ~ 5.0 quality % in this catalyst, metal active constituent is platinum rhenium or platinum tin, and carrier is aluminium oxide.Although the introducing of phosphorus can improve catalyst performance, activity stability still has much room for improvement.
CN201080030122.5 discloses a kind of preparation method had close to the multimetal reforming catalyst optimizing site, comprise the promoter X1 that at least one platinum group metal, tin, phosphorus accelerant, halogenated compound, porous carrier and at least one are selected from gallium, indium, thallium, arsenic, antimony and bismuth, promoter X1 and phosphorus first introduce in aluminium oxide by described method, tin is together introduced with it, reshaping, platinum group metal is introduced after roasting, be no more than drying under the temperate condition of 150 DEG C, 350 ~ 650 DEG C of roastings obtain catalyst.This catalyst is a kind of continuous reforming catalyst, can improve C
5 +product selective, coke content significantly reduces simultaneously.
Summary of the invention
The object of this invention is to provide a kind of semi regeneration reforming catalyst and preparation method thereof, this catalyst has higher activity and arenes selectivity and catalyst regeneration performance.
Semi regeneration reforming catalyst provided by the invention, comprises phosphorus-containing alumina carrier and with the following active component of the butt aluminium oxide content that is benchmark:
Phosphorus content in described phosphorus-containing alumina with butt aluminium oxide for benchmark counts 0.01 ~ 3.0 quality %.
The present invention is load VIII race metal, VII B race metal and III A race metal in phosphorous alumina support, due to adding of III A race metal and phosphorus, catalyst choice is improved, and product liquid is received to be increased, and catalyst regeneration ability strengthens.Make catalyst can obtain better reactivity worth under the operating condition of high temperature, low pressure and low hydrogen/gasoline ratio.
Detailed description of the invention
The present invention introduces active metal and modified metal-III A race metal in phosphorous alumina support, can significantly improve the performance of semi regeneration reforming catalyst, liquid product yield is increased, and combination property is improved, regenerability improves, and the performance of regenerated catalyst is recovered substantially.
Active component content described in catalyst of the present invention is preferably:
Phosphorus content in described phosphorus-containing alumina with butt aluminium oxide for benchmark counts 0.05 ~ 1.0 quality %.
In catalyst of the present invention, the amount of phosphorus and active metal should control in optimum range, preferably, the mass ratio of phosphorus and VIII race's metal is 0.2 ~ 5.0, preferably 0.5 ~ 3.0, the mass ratio of phosphorus and VII B race metal is 0.2 ~ 4.0, preferably 0.2 ~ 2.0, and the mass ratio of phosphorus and III A race metal is 0.5 ~ 6.0, preferably 1.0 ~ 4.0.
The preferred gama-alumina of aluminium oxide of the present invention, the gama-alumina more preferably prepared by the high purity aluminium hydroxide that aluminum alkoxide hydrolysis is obtained.
The shape of carrier of the present invention can be spherical, bar shaped, sheet, graininess or trifolium-shaped, preferred bar shaped, spherical or cloverleaf pattern.
The described preferred platinum of VIII race's metal, the preferred rhenium of VII B race metal, the preferred chlorine of halogen, the III described preferred gallium of A race metal or indium.
The method preparing catalyst of the present invention first prepares phosphorus-containing alumina, and then dipping introduces other active component.
The preparation method of catalyst of the present invention comprises and first prepares phosphorus-containing alumina carrier, again with containing VIII race's metallic compound, containing VII B race metallic compound and the solution impregnation phosphorus-containing alumina carrier containing III A race metallic compound and halogen, carrying out presulfurization by hydrogen sulfide containing hydrogen treat after drying, roasting, reduction.
Described phosphorous aluminium oxide can adopt extruded moulding legal system to be in strip, or adopts Alumina gel oil column spherical container shaping method to make spherical.
The preparation method of described bar shaped phosphorus-containing alumina is: in aluminium hydrate powder, add phosphorus-containing compound and the abundant kneading of peptizing agent, extruded moulding, dry, roasting.
The method that extruded moulding prepares phosphorus-containing alumina carrier is preferably: mixed with appropriate extrusion aid by aluminium hydrate powder, add peptizing agent and phosphorus-containing compound kneading, extruded moulding again, 30 ~ 80 DEG C of dryings 2 ~ 24 hours, 90 ~ 200 DEG C of dryings 2 ~ 24 hours, the phosphorus-containing alumina carrier of 400 ~ 800 DEG C, preferably 550 ~ 700 DEG C roasting obtained bar shaped in 2 ~ 24 hours.Described extrusion aid is sesbania powder, and the mass ratio of extrusion aid and aluminium hydrate powder is 0.01 ~ 0.50:1.Peptizing agent be selected from nitric acid, citric acid, acetic acid, hydrochloric acid and sulfuric acid one or more.Concentration preferably 0.1 ~ 10.0 quality % of contained acid in peptizing agent.The mass ratio of peptizing agent and aluminium hydrate powder is 0.5 ~ 1.2:1.
The preparation method of described spherical phosphorus-containing alumina is: solid content be 15 ~ 50 quality %, aluminium/cl molar ratio is add phosphorus-containing compound in the Alumina gel of 0.5 ~ 3.0:1 to mix, ball forming is dripped in deep fat post or oil ammonia column, then by the bead after shaping at 90 ~ 150 DEG C, under the condition of 0.2 ~ 0.6MPa aging 2 ~ 24 hours, in 60 ~ 150 DEG C of dryings 2 ~ 24 hours after washing, 400 ~ 800 DEG C, preferably 550 ~ 700 DEG C roasting obtains spherical phosphorus-containing alumina.
Described deep fat post or the temperature of oil ammonia column are 60 ~ 150 DEG C.The method preparation of Alumina gel acceptable salts acid dissolve metallic aluminium used in preparation process, also available hydrogen alumina powder adds appropriate peptizing agent, as watery hydrochloric acid preparation, or is that parent prepares Alumina gel with aluminium polychloride.
In above-mentioned phosphorous carrying alumina production procedure, the sintering temperature of carrier preferably 450 ~ 650 DEG C.In order to obtain high-specific surface area, preferably carry out under the environment having suitable quantity of water to exist during roasting, the water content of roasting medium is 0.1 ~ 20 quality %, preferably 2 ~ 15 quality %, more preferably 10 ~ 15 quality %.
Prepare phosphorus-containing alumina phosphorus-containing compound used and be preferably phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, codehydrogenase II, triphenylphosphine, phosphorus trichloride, tributyl phosphoxide, tributyl phosphite, phosphorus tribromide, triiodo phosphorous oxide, phosphorous oxychloride, triphenylphosphine or phosphorus tribromide, more preferably phosphoric acid or phosphorus trichloride.
The present invention adopts the method for total immersion to introduce metal active constituent, and what preparation maceration extract was used contains the preferred chloroplatinic acid of VIII race's metallic compound, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride carbonyl platinum, dinitro diaminourea platinum or tetranitro sodium platinate.Used contains the preferred perrhenic acid of VII B race metallic compound, ammonium perrhenate or potassium perrhenate.Compound containing the III preferred gallium of A race metallic compound or indium used is as follows:
Used containing gallium compound is: Ga
2(CO
3)
3, GaCl
3, Ga (OH)
3, Ga (NO
3)
3, Ga
2o
3or Ga
2(SO
4)
3,
Used containing In compound is: In
2(CO
3)
3, InCl
3, In (OH)
3, In (NO
3)
3, In
2o
3or In
2(SO
4)
3, preferred InCl
3, In (NO
3)
3.
More preferably the nitrate of gallium or indium or chloride.
The present invention also can adopt step impregnation method to introduce catalytic active component, and after each dipping introduces a kind of active component, through super-dry, roasting, then introduce another kind of component, VIII race's metal is introduced in preferred final step.
Dipping is introduced the method for active component and be can be saturated dipping or supersaturation dipping, Gu the liquid/volume ratio of maceration extract and carrier is less than 1.0 during saturated dipping, and preferably 0.5 ~ 0.9, maceration extract loaded body absorbs completely.Gu liquid/volume ratio that maceration extract used and carrier are flooded in supersaturation is greater than 1.0, preferably 1.1 ~ 3.0, maceration extract superfluous after dipping is by filtering or the method removing of vacuum evaporating solvent.Described dipping temperature is 20 ~ 60 DEG C, preferably 20 ~ 40 DEG C.
The method of described vacuum evaporating solvent can adopt rotary vacuum evaporator to carry out, concrete method of operating is: the water soluble compound containing each active component is mixed with maceration extract, phosphorous aluminium oxide is flooded under the condition of 0.001 ~ 0.10MPa and rotation, Gu the liquid/volume ratio of maceration extract and phosphorous aluminium oxide is 1.1 ~ 3.0, linear velocity is 0.01 ~ 2.0 meter per second, carries out drying and calcination activation after dipping.The pressure preferably 0.001 ~ 0.08MPa of vacuum rotating dipping.During dipping, limit heating edge rotates, heating-up temperature and dipping temperature preferably 20 ~ 90 DEG C, more preferably 30 ~ 70 DEG C, and the speed of rotation should not be too fast, and preferred linear velocity is 0.02 ~ 0.8 meter per second, more preferably 0.03 ~ 0.5 meter per second.Dip time preferably 1 ~ 8 hour, more preferably 2 ~ 4 hours.After vacuum rotating dipping, in maceration extract, moisture evaporates substantially, and catalyst is drying regime, now directly can be taken out by carrier and carry out drying and calcination activation.
The for the benefit of introducing of halogen component and metal component being uniformly distributed on whole carrier, preferably add competitive adsorbate in dipping solution.Preferred competitive adsorbate is HCl or trichloroacetic acid, both can add maceration extract respectively, also can add maceration extract simultaneously, in maceration extract, the mass ratio of HCl and trichloroacetic acid is 0.01 ~ 50:1, preferably 0.2 ~ 10:1, the concentration of competitive adsorbate in maceration extract counts 0.2 ~ 3.0 quality % with chlorine, preferably 0.8 ~ 2.0 quality %.If adding trichloroacetic acid in maceration extract is competitive adsorbate, after carrier drying, preferably 150 ~ 230 DEG C of heating 0.5 ~ 24 hour, to make trichloroacetic acid desorption from carrier.
Catalyst of the present invention before use must through presulfurization.In sulfuration rear catalyst, sulfur content is 0.01 ~ 0.5%, is preferably 0.04 ~ 0.2%(relative to catalyst quality).
Catalyst of the present invention is suitable for catalytic reforming reaction.Reformer feed to be boiling range the be naphtha of 40 ~ 230 DEG C, as straight-run naphtha, hydrocracked naphtha, cat cracked naphtha, hydrogenation coking naphtha and hydrogenation coal liquefaction naphtha.The reaction condition that catalyst of the present invention is suitable for is: 0.1 ~ 10.0MPa, preferably 0.5 ~ 3.0MPa, 370 ~ 600 DEG C, preferably 450 ~ 550 DEG C, hydrogen/hydrocarbon volume ratio 300 ~ 1000, preferably 500 ~ 1500, during feedstock quality air speed 0.1 ~ 20.0
-1, preferably 0.5 ~ 3.0 time
-1.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
Following instance prepares the phosphorous γ of bar shaped-Al
2o
3carrier.
(German Sasol company produces to get 100 grams of SB powder, alumina content is 75 quality %) mix with 2.0 grams of sesbania powder, the phosphoric acid that the nitric acid being 98.0 quality % with 65.0 milliliters of deionized waters, 1 ml concn, 0.7 ml concn are 85.0 quality %, 4 grams of citric acids, 4 milliliters of acetic acid are made into phosphorous peptizing agent, add kneading in the SB powder mixed with sesbania powder, then the orifice plate extruded moulding of 1.6mm is adopted, 60 DEG C of dryings 12 hours, 120 DEG C of dryings 12 hours, 650 DEG C of roastings 4 hours, obtain the γ-Al of phosphorous 0.4 quality %
2o
3carrier ZT-1.
By above-mentioned obtained carrier in 820 DEG C of roastings 24 hours, investigate its heat endurance.
By above-mentioned obtained carrier in 650 DEG C, controlling air is 700/1 with the gas agent ratio of carrier, passes into 0.02MPa steam treatment 80 hours, makes water content in air be 13.85 quality %, investigates the hydrothermal stability of carrier.
The specific area of carrier ZT-1 and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Example 2
Phosphorous γ-Al is prepared by the method for example 1
2o
3carrier is 1.1 milliliters unlike phosphoric acid amount used, obtains the γ-Al of phosphorous 0.6 quality %
2o
3carrier ZT-2, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Example 3
Phosphorous γ-Al is prepared by the method for example 1
2o
3carrier is 1.8 milliliters unlike phosphoric acid amount used, obtains the γ-Al of phosphorous 1.0 quality %
2o
3carrier ZT-3, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Example 4
Phosphorous γ-Al is prepared by the method for example 1
2o
3carrier is 5.3 milliliters unlike phosphoric acid amount used, obtains the γ-Al of phosphorous 3.0 quality %
2o
3carrier ZT-4, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Example 5
Phosphorous γ-Al is prepared by the method for example 1
2o
3carrier, unlike adding 1.33 grams of phosphorus trichlorides in peptizing agent, obtains the γ-Al of phosphorous 0.4 quality %
2o
3carrier ZT-5, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Example 6
This example adopts the oil ammonia column method of forming to prepare spherical phosphorous γ-Al
2o
3carrier.
Be the dissolving with hydrochloric acid of 23.0% at 90 DEG C by concentration by aluminium ingot, 90 DEG C of refining deferrizations 6 hours, obtained solid content is 36.0 quality %, aluminium/cl molar ratio is the Alumina gel of 1.60.Joined in Alumina gel by phosphoric acid and mix, phosphoric acid addition should make phosphorus content be that 0.6 quality %(is relative to butt quality of alumina).In 95 DEG C, Alumina gel is instilled balling-up in oil ammonia column, oil column upper oil phase is white oil, the ammoniacal liquor of lower floor's aqueous phase to be concentration be 5.0 quality %.Collect ammoniacal liquor mutually in bead, at 120 DEG C, under the condition of 0.35MPa aging 6 hours, then wash, 60 DEG C of dryings 12 hours, 120 DEG C of dryings 6 hours, 650 DEG C of roastings 4 hours, obtained spherical phosphorous γ-Al
2o
3carrier ZT-6, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Comparative example 1
Prepare carrier by the method for example 1, do not add phosphoric acid unlike in peptizing agent, obtained γ-Al
2o
3carrier ZTDB-1, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Comparative example 2
Prepare ball type carrier by the method for example 6, do not add phosphoric acid unlike in Alumina gel, obtained spherical gamma-Al
2o
3carrier ZTDB-2, its specific area and the specific area after 820 DEG C of roastings and 650 DEG C of hydrothermal treatment consists are in table 1.
Example 7
The method of total immersion stain is adopted to prepare phosphorous Pt-Re-Ga catalyst.
Get phosphorous carrier ZT-1 prepared by 50 grams of examples 1, chloroplatinic acid, perrhenic acid, gallium nitrate and hydrochloric acid are made into maceration extract, make to contain Pt0.24%, Re0.52%, Ga0.50%, Cl1.8%(in maceration extract all relative to the quality of butt aluminium oxide), Gu liquid/volume ratio is 1.9.25 DEG C of dippings filtered after 24 hours, 60 DEG C of dryings 6 hours, 120 DEG C of dryings 12 hours, in dry air in 500 DEG C, gas/agent volume ratio be the condition of 700 under calcination activation 4 hours, then in 480 DEG C, gas/agent volume ratio uses H under being the condition of 500
2reduce 4 hours, finally 425 DEG C, add 0.16%(relative to catalyst quality in hydrogen stream) hydrogen sulfide presulfurization is carried out to catalyst, obtain catalyst Cat-1, its composition is in table 2.
Example 8
Get phosphorous carrier ZT-2 prepared by 50 grams of examples 2, chloroplatinic acid, ammonium perrhenate, gallium chloride and hydrochloric acid are made into maceration extract, make to contain Pt0.24%, Re0.41%, Ga0.31% and Cl1.8%(in maceration extract relative to butt quality of alumina), Gu liquid/volume ratio is 1.5.Carrier and maceration extract are poured in 500 ml flasks, in rotary vacuum evaporator (Shanghai Yarong Biochemical Instrument Plant's production) in 30 DEG C, 0.008MPa, rotation linear speed 0.03 meter per second rotating speed under dipping 3 hours, solid is made to be dry shape under 70 DEG C of decompressions, 120 DEG C of dryings 12 hours.In dry air in 500 DEG C, gas/agent volume ratio be the condition of 700 under activation 4 hours, then in 480 DEG C, gas/agent volume ratio uses H under being the condition of 500
2reduce 4 hours, finally 425 DEG C, add 0.16%(relative to catalyst quality in hydrogen stream) hydrogen sulfide presulfurization is carried out to catalyst, obtain catalyst Cat-2, its composition is in table 2.
Example 9
According to the method Kaolinite Preparation of Catalyst of example 7, replace gallium nitrate unlike during preparation maceration extract with indium nitrate, make maceration extract contain the indium (quality relative to butt aluminium oxide) of 0.42%, the composition of obtained catalyst Cat-3 is in table 2.
Example 10
According to the method Kaolinite Preparation of Catalyst of example 8, replace gallium chloride unlike during preparation maceration extract with inidum chloride, make the indium (quality relative to butt aluminium oxide) containing 0.15% in maceration extract, the composition of obtained catalyst Cat-4 is in table 2.
Example 11
According to the method Kaolinite Preparation of Catalyst of example 8, maceration extract is made into unlike by chloroplatinic acid, ammonium perrhenate, gallium chloride, inidum chloride and hydrochloric acid, make to contain Pt0.22%, Re0.46%, Ga0.2%, In0.15 and Cl1.8%(in maceration extract relative to butt quality of alumina), the composition of obtained catalyst Cat-5 is in table 2.
Example 12
According to the method Kaolinite Preparation of Catalyst of example 10, be spherical phosphorous γ-Al unlike used carrier
2o
3carrier ZT-6, the composition of obtained catalyst Cat-6 is in table 2.
Example 13
Get γ-Al prepared by 50 grams of comparative examples 1
2o
3carrier ZTDB-1 is the solution impregnating carrier 3 hours of 0.0084 quality % with 75 milliliters of phosphoric acid concentrations, and 120 DEG C of dryings 12 hours, 500 DEG C of roastings obtain the carrier of phosphorous 0.4 quality % for 2 hours.Get this carrier, according to the method Kaolinite Preparation of Catalyst of example 10, obtain catalyst Cat-4a, its composition is in table 1.
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of example 8, be bar shaped γ-Al unlike used carrier
2o
3carrier ZTDB-1, the composition of obtained catalyst CatDB-1 is in table 2.
Comparative example 4
According to the method Kaolinite Preparation of Catalyst of example 8, be spherical gamma-Al unlike used carrier
2o
3carrier ZTDB-2, replace gallium chloride unlike during preparation maceration extract with inidum chloride, make the indium (quality relative to butt aluminium oxide) containing 0.15% in maceration extract, the composition of obtained catalyst CatDB-2 is in table 2.
Comparative example 5
By the method Kaolinite Preparation of Catalyst of example 7, do not contain gallium unlike in maceration extract used, the composition of obtained catalyst CatDB-3a is in table 2.
Comparative example 6
According to the method Kaolinite Preparation of Catalyst CatDB-3 of Chinese patent CN201080030122.5 example 4, the carrier of use is bar shaped γ-Al
2o
3carrier ZTDB-1, impregnation fluid carrier is mixed with phosphoric acid, indium nitrate and stannous chloride, make to contain Sn0.3%, In0.3%, P0.4%(in maceration extract relative to butt quality of alumina), then in 500 DEG C of roastings 2 hours, again with chloroplatinic acid and aqueous hydrochloric acid solution dipping, make containing Pt0.24 quality %, Cl1.0 quality %, after dipping, solid was in 500 DEG C of roastings 4 hours, obtained catalyst CatDB-3, its composition is in table 2.
Comparative example 7
Prepare carrier by the method for example 1, also contain gallium nitrate unlike in the peptizing agent of preparation, make the P contained in peptizing agent be 0.4 quality %, gallium is that 0.4 quality %(is all relative to butt quality of alumina), obtained carrier ZTDB-3.Get 50 grams, this carrier, by the method Kaolinite Preparation of Catalyst of example 7, be made into maceration extract unlike by chloroplatinic acid, perrhenic acid and hydrochloric acid, make to contain Pt0.24%, Re0.52%, Cl1.8%(in maceration extract all relative to butt quality of alumina), obtain catalyst CatDB-4, its composition is in table 2.
Example 14
On 100 milliliters of devices, with refining naphtha for raw material is evaluated catalyst of the present invention and comparative catalyst, appreciation condition is: 520 DEG C, 0.69MPa, feedstock quality air speed 2.0 time
-1, hydrogen/hydrocarbon volume ratio 1000:1,140 hours reaction time.Evaluate raw materials used oil nature in table 3, evaluating catalyst the results are shown in Table 4.Under identical octane number (RON), the liquid yield height of catalyst illustrates that it is selective good.Octane number yield (product of liquid yield and octane number) is high, illustrates that the combined reaction performance of catalyst is good.
From table 4 data, catalyst of the present invention is than comparative example, and liquid yield, octane number yield and aromatics yield (virtue produces) are all higher, illustrate that catalyst of the present invention has higher catalytic activity and arenes selectivity.
Example 15
Cat-3, Cat-4a and CatDB-3a of reacting inactivation in example 14 are carried out that routine is burnt, after chlorination renewal and reducing/regenerating, then adopts the method for example 14 to regenerated catalyst evaluation, the results are shown in Table 4.
From table 4 data, catalyst of the present invention, than comparative catalyst CatDB-3a, has preferably regenerability.
Table 1
Table 2
Note: in catalyst composition, constituent content is the content relative to butt aluminium oxide.
Table 3
Table 4
| Catalyst is numbered | Liquid yield, quality % | RON | Octane number yield, % | Virtue produces, quality % |
| Cat-1 | 85.43 | 100.8 | 86.1 | 63.5 |
| Cat-2 | 85.66 | 101.0 | 86.5 | 64.2 |
| Cat-3 | 86.69 | 100.7 | 87.3 | 64.3 |
| Cat-4 | 86.89 | 100.8 | 87.6 | 64.6 |
| Cat-5 | 86.70 | 101.3 | 87.8 | 65.0 |
| Cat-6 | 86.58 | 100.9 | 87.4 | 64.5 |
| Cat-4a | 85.67 | 100.4 | 86.1 | 62.8 |
| CatDB-1 | 84.45 | 100.1 | 84.6 | 61.0 |
| CatDB-2 | 85.01 | 100.2 | 85.2 | 61.6 |
| CatDB-3a | 85.22 | 100.2 | 85.4 | 61.7 |
| CatDB-3 | 85.36 | 100.0 | 85.3 | 61.5 |
| CatDB-4 | 85.47 | 100.0 | 85.4 | 61.6 |
| After Cat-3 regeneration | 86.73 | 100.8 | 87.4 | 64.4 |
| After Cat-4a regeneration | 85.71 | 100.3 | 85.9 | 62.5 |
| After CatDB-3a regeneration | 85.56 | 100.1 | 85.6 | 61.6 |
Claims (14)
1. a semi regeneration reforming catalyst, comprises phosphorus-containing alumina carrier and with the following active component of the butt aluminium oxide content that is benchmark:
Phosphorus content in described phosphorus-containing alumina with butt aluminium oxide for benchmark counts 0.01 ~ 3.0 quality %.
2., according to catalyst according to claim 1, it is characterized in that the content of described each active component is:
Phosphorus content in described phosphorus-containing alumina with butt aluminium oxide for benchmark counts 0.05 ~ 1.0 quality %.
3. according to catalyst according to claim 1, it is characterized in that the mass ratio of phosphorus and VIII race's metal in catalyst is 0.2 ~ 5.0, the mass ratio of phosphorus and VII B race metal is 0.2 ~ 4.0, and the mass ratio of phosphorus and III A race metal is 0.5 ~ 6.0.
4., according to the catalyst described in claim 1 or 2, it is characterized in that described aluminium oxide is gama-alumina.
5., according to the catalyst described in claim 1 or 2, it is characterized in that VIII described race's metal is platinum, VII B race metal is rhenium, and halogen is chlorine.
6., according to the catalyst described in claim 1 or 2, it is characterized in that III described A race metal is gallium or indium.
7. the preparation method of catalyst described in a claim 1, comprise and first prepare phosphorus-containing alumina carrier, again with containing VIII race's metallic compound, containing VII B race metallic compound and the solution impregnation phosphorus-containing alumina carrier containing III A race metallic compound and halogen, carrying out presulfurization by hydrogen sulfide containing hydrogen treat after drying, roasting, reduction.
8. in accordance with the method for claim 1, it is characterized in that described phosphorus-containing alumina is bar shaped or spherical.
9. in accordance with the method for claim 8, it is characterized in that the preparation method of bar shaped phosphorus-containing alumina is: the abundant kneading of peptizing agent adding phosphorus-containing compound in aluminium hydrate powder, extruded moulding, dry, roasting.
10. in accordance with the method for claim 9, it is characterized in that described phosphorus-containing compound is phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, codehydrogenase II, triphenylphosphine, phosphorus trichloride, tributyl phosphoxide, tributyl phosphite, phosphorus tribromide, triiodo phosphorous oxide, phosphorous oxychloride, triphenylphosphine or phosphorus tribromide, peptizing agent be selected from nitric acid, citric acid, acetic acid, hydrochloric acid and sulfuric acid one or more.
11. in accordance with the method for claim 7, it is characterized in that the preparation method of spherical phosphorus-containing alumina is: solid content be 15 ~ 50 quality %, aluminium/cl molar ratio is add phosphorus-containing compound in the Alumina gel of 0.5 ~ 3.0:1 to mix, ball forming is dripped in deep fat post, then by the bead after shaping at 90 ~ 150 DEG C, under the condition of 0.2 ~ 0.6MPa aging 2 ~ 24 hours, in 60 ~ 150 DEG C of dryings 2 ~ 24 hours after washing, 400 ~ 800 DEG C of roastings obtain spherical phosphorus-containing alumina.
12. in accordance with the method for claim 7, it is characterized in that described is chloroplatinic acid, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride carbonyl platinum, dinitro diaminourea platinum or tetranitro sodium platinate containing VIII race's metallic compound.
13. in accordance with the method for claim 7, it is characterized in that described is perrhenic acid, ammonium perrhenate or potassium perrhenate containing VII B race metallic compound.
14. in accordance with the method for claim 7, it is characterized in that described is nitrate or the chloride of gallium or indium containing III A race metallic compound.
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