CN1044377C - Preparation of reforming platinum-rhenium catalyst - Google Patents
Preparation of reforming platinum-rhenium catalyst Download PDFInfo
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- CN1044377C CN1044377C CN96103410A CN96103410A CN1044377C CN 1044377 C CN1044377 C CN 1044377C CN 96103410 A CN96103410 A CN 96103410A CN 96103410 A CN96103410 A CN 96103410A CN 1044377 C CN1044377 C CN 1044377C
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Abstract
The present invention relates to a preparing method for a platinum-rhenium reforming catalyst. In the present invention, nitric acid with the weight percentage of 0.1 to 5.0 wt% of aluminium hydrate powder, acetic acid with the weight percentage of 1.0 to 10.0% of the aluminium hydrate powder, and citric acid with the weight percentage of 2.0 to 10.0% of the aluminium hydrate powder are mixed to prepare a water solution used as a peptizing agent. The peptizing agent is added into the aluminium hydrate powder mixed with 0.1 to 4.0 wt% of sesbania powder to be kneaded and extruded. Drying and roasting are carried out to obtain a strip-shaped gamma-Al2O3 carrier. Then, Pt with the weight percentage of 0.10 to 0.80 wt% of dry basis aluminum oxide, Re with the weight percentage of 0.10 to 0.50 wt% of the dry basis aluminum oxide and Cl with the weight percentage of 0.5 to 2.0 wt% of the dry basis aluminum oxide are loaded to obtain the catalyst. The catalyst is suitable for the reformation of virgin naphtha with the distillation range of 60 to 210 DEG C or the reformation of gasoline which is produced by technologies, such as coking, cracking, etc., in blending petroleum processing and has the distillation range of 60 to 210 DEG C.
Description
The present invention is a kind of preparation method of catalyst for reforming naphtha, specifically.Be a kind of preparation method of bar shaped platinum-rhenium reforming catalyst.
After nineteen sixty-eight, United States Patent (USP) 3,415,737 proposed platinum rhenium dual metal reforming catalyst, platinum-reforming catalyst began to enter a new developmental stage.Afterwards, United States Patent (USP) 4,356,081 proposes high rhenium platinum again has better properties than the reforming catalyst of (2～5), and platinum-rhenium reforming catalyst is further developed.At present, platinum-rhenium reforming catalyst becomes one of catalyzer that is most widely used in the full scale plant with its good stability that has.
But platinum-rhenium reforming catalyst still has some deficits, thus people mainly catalyzer have been carried out improving one aspect following two be the prescription that improves platinum-rhenium catalyst, as improving rhenium platinum ratio.Add metal promoter etc.; Another main means are to improve the performance of support of the catalyst.Reforming catalyst carrier commonly used has γ-Al
2O
3And η-Al
2O
3Because preparation method's difference of aluminum oxide, its performance also has very big-difference, thereby also can impact catalyst performance, as United States Patent (USP) 4,178,268 adopt the SB preparation of aluminium hydroxide support of the catalyst of the synthetic by-product of Ziegler, and the HP aluminium hydroxide that CN1032951A adopts the low-carbon alkoxy aluminium hydrolysis to get is feedstock production γ-Al
2O
3Carrier; Owing to adopted the high alumina supporter of purity, made the catalyzer of preparation have good activity, selectivity and stable and for example CN1055192A with aluminium hydroxide raw material refabrication γ-Al after carrying out aqueous vapor atmosphere acidification under 60～250 ℃ the temperature
2O
3Carrier also makes activity of such catalysts, selectivity and stability increase.
Except the preparation method of aluminum oxide produces considerable influence its performance, the forming method of alumina supporter also exerts an influence to its performance.Common forming method has the ball and the extrusion of dripping, extrusion technology mainly comprise mix pinch, steps such as extrusion, pelletizing, drying, roasting are with respect to the preparation technology of ball-type carrier, it is simple to have technology, advantages such as low cost of manufacture, but to the bar shaped carrier, require it that bigger intensity should be arranged, otherwise insufficient strength, in use will crush and cause the raising of beds pressure drop.In existing extrusion technology, often need to add peptizing agent in the kneading process, peptizing agent commonly used is nitric acid or acetate, as United States Patent (USP) 4,178,268 introductions prepare the bar shaped carrier with the nitric acid or the acetate that account for butt alumina weight 2～7% as peptizing agent, and CN1032951A introduces with the nitric acid that accounts for alumina weight 4% and prepares γ-Al as peptizing agent
2O
3Carrier; CN1056514A has then introduced with nitric acid and citric acid and has made the aluminum oxide bar shaped carrier that the peptizing agent preparation contains a small amount of zeolite, and this carrier is used to prepare hydrotreating catalyst.
In a word, in the prior art, make peptizing agent, extrude bar poor toughness, easily broken, embrittlement with nitric acid; Make peptizing agent with acetate and citric acid, extrude soft, the easy adhesion cutting of bar difficulty.And the bar shaped support strength of method for preparing is not good enough.
The object of the present invention is to provide a kind of system of bar shaped catalyst to put forth energy method, make the catalyzer that makes with this method have higher intensity, and activity, stability and selectivity are preferably arranged.
The preparation method of bar shaped catalyst provided by the invention is: in aluminium hydrate powder, adds the sesbania powder account for its weight 0.1～4.0% and stirs evenly, and again with accounting for aluminium hydrate powder weight 0.1～5.0%, 0.5～1.5% nitric acid preferably; 1.0～10.0%, 2.0～4.0% acetate preferably; 2.0～10.0%, preferably the mixed solution of 3.0～6.0% citric acid composition is made into peptizing agent, and this peptizing agent is poured in the aluminium hydrate powder, and kneading is to being the plastic shape, 60～80 ℃ of dryings of extruded moulding are 4～10 hours then, 100～130 ℃ of dryings 6～24 hours; 450～800 ℃, preferably 550～650 ℃ of roastings made γ-Al in 2～12 hours
2O
3Carrier, load accounts for butt alumina weight 0.10～0.8% again, preferably 0.2～0.4% Pt; 0.10～1.50%, preferably 0.2～0.8% Re and 0.5～2.0%, preferably 0.8～1.5% Cl makes catalyzer.The RePt weight ratio is 0.5～4.0 in the catalyzer, preferably 1.0～3.0.
The high purity aluminium hydroxide that described aluminium hydroxide gets for the aluminum alkoxide hydrolysis.
Abnormity such as that the shape of described bar shaped carrier comprises is cylindrical, trilobal, quatrefoil.
Catalyzer adopts conventional common leaching method preparation: with the platinic compound of predetermined amount, preferably Platinic chloride or ammonium chloroplatinate; Rhenium compound, preferably perrhenic acid or ammonium perrhenate; Hydrochloric acid and deionized water are mixed and made into steeping fluid, and the volume ratio of steeping fluid and carrier is 1.0～2.5.At room temperature flood bar shaped γ-Al
2O
3Carrier 12～24 hour, filter, soak the back bar 60～80 ℃ of dryings 6～10 hours, 100～130 ℃ of dryings 12～24 hours, 450～550 ℃, gas agent volume ratio are activation in 500～1200 o'clock 2～12 hours in the dry air, 400～500 ℃, gas agent volume ratio are activation in 500～1200 o'clock 2～12 hours in hydrogen afterwards, afterwards 400～500 ℃ of reductase 12～12 hour in hydrogen.
Another constituent element of catalyzer is the halogen that comprises fluorine, chlorine, and is best with chlorine.Introducing mode preferably be the form of or Organohalogen compounds inorganic with hydrochloric acid or other when dipping and the metal constituent element together introduce.
This catalyzer must be 0.01～1.00% through sulphur content in the prevulcanized sulfuration rear catalyst before use, preferably 0.04～1.0% (with respect to catalyst weight).
Can be used for virgin naphtha that boiling range is 60～210 ℃ (press the GB-255 methods analyst, down with) or its with the catalyzer of the inventive method preparation, to admix the boiling range of explained hereafter such as coking in refining of petroleum, cracking be the reforming process of 60～210 ℃ gasoline.The reforming process of particularly suitable virgin naphtha.
The present invention is because employing nitric acid, acetate and citric acid are that peptizing agent prepares bar shaped γ-Al
2O
3Carrier, supporting Pt, Re metal active constituent are made catalyzer again.It is good to have extruded moulding, the carrier crushing strength height of preparation (reach 130～140 newton/centimetre), advantage such as middle pore distribution concentration, pore structure are stable.The catalyzer that makes thus has high activity and arenes selectivity, and coke content is low.Good stability.As on middle-scale device, to estimate with the same terms, catalyzer of the present invention is compared with external import catalyzer (E-803).Virtue produces high 2.3 heavy %, transformation efficiency high 5.4 heavy %.
Further specify the present invention below by example.
Example 1
The preparation method of this case introduction bar shaped carrier.
Get 100 gram SB aluminum hydroxide solid elastomer powder (German Condea company), 2 gram sesbania powder stir evenly after the mixing.Get 1.4 grams, 65% nitric acid (Beijing Chemical Plant, analytical pure), 7.3 grams, 36% acetate (Tianjin chemical reagent one factory, analytical pure), 4 gram citric acids (Beijing Chemical Plant, chemical pure), 70 gram decationized Y sieve water are made into peptizing agent after mixing, this peptizing agent is poured in the dry glue powder of mixing, kneading is to being the plastic shape, on banded extruder, be extruded into cylindric vertical bar, extrude bar, 120 ℃ of dryings 12 hours 60 ℃ of dryings 6 hours, roasting is 8 hours in 650 ℃ of air, obtains bar shaped γ-Al
2O
3Carrier a-1.
Example 2
Method by example 1 prepares bar shaped γ-Al
2O
3Carrier a～2, different is the dosage difference of various acid in the peptizing agent, concrete prescription sees Table 1.
Comparative Examples 1
The prescription of example 4 among the imitative CN1056514A does not use nitric acid and citric acid but do not add the zeolite peptizing agent.Get 100 gram SB dry glue powders, prepare γ-Al by the method for example 1
2O
3Carrier b-1.Each material formula sees Table 1 during preparation.
Comparative Examples 2～4
Press USP4, the optimum range of used nitric acid and/or acetate during extrusion in 178,268 prepares carrier b-2, b-3, b-4 by the method for example 1, and the used peptizing agent prescription of each carrier sees Table 1.
Comparative Examples 5～6
Comparative Examples 5 is that peptizing agent prepares carrier b-5 with acetate and citric acid.Comparative Examples 6 is that peptizing agent prepares carrier b-6 with the citric acid.The used peptizing agent prescription of two carriers sees Table 1.
Example 3
The carrier for preparing in the support of the catalyst of this case introduction the present invention preparation and the Comparative Examples and the intensity contrast of external import bar shaped platinum-rhenium catalyst, specific surface and pore structure contrast.
E-603, E-803 that said external import bar shaped catalyst is a U.S. Engdlhard company.The intensity contrast data see Table 2, the broken intensity of intensity finger pressure wherein, and its measuring method is: get 5 millimeters long vertical bars, in the radially crushing strength of intelligent granule strength test aircraft measurements simple grain bar.Every batch sample is measured 12 times, gets the mean value of 10 intermediate data.Table 2 shows that the carrier (a-1, a-2) of the present invention's preparation has higher crushing strength.
Specific surface and pore structure correlation data see Table 3, and its numerical value adsorbs on the instrument automatically at 1822 type cryogenic nitrogens to be measured.As shown in Table 3, have bigger specific surface, and pore radius is that the middle pore distribution of 30-50A is more, illustrate that pore structure is better than contrasting sample, particularly be better than making the carrier b-2 that peptizing agent prepares with nitric acid with the carrier of the inventive method preparation.
Example 4
This case introduction Preparation of catalysts.
Get the carrier a-1 of preparation in the 60 gram examples 1, Platinic chloride (Chang Ling catalyst plant with predetermined amount, analytical pure), perrhenic acid (Wuhan specialty oil products factory, analytical pure) and hydrochloric acid (Red Star chemical plant, Beijing, analytical pure) is made into steeping fluid, contain Pt0.24%, Re0.26%, Cl1.49% (with respect to the butt alumina weight) in this steeping fluid, steeping fluid is 1.2 with the carrier bulk ratio.24 hours after-filtration of dipping under the room temperature, 60 ℃ of dryings 6 hours, 120 ℃ of dryings 12 hours, 500 ℃, gas agent volume ratio are activation in 700 o'clock 4 hours in the dry air, H
2In 480 ℃ of reduction made catalyzer c-1 in 4 hours.Carry out prevulcanized then and handle, promptly at H
2Till adding hydrogen sulfide to beds penetrated in the stream, catalyzer all carried out the prevulcanized processing with this method in the following example.
C-2 Preparation of catalysts method is same as c-1 substantially, but the Rt in the catalyzer, Re, Cl content difference.
C-3 Preparation of catalysts method is same as c-1 substantially, and different is that carrier is a-2, Pt, Re, Cl content difference in the catalyzer.
C-4 is the comparative catalyst, and used carrier is the b-2 in the Comparative Examples 2, and the preparation method is basic in c-1, but Pt, Re, Cl content difference in the catalyzer.
More than each catalyzer form and list in the table 4, wherein Pt, Re, content spectrophotometric analysis, Cl content is with the analysis of ion specific electrode method.
Pt, the Re content of two other comparative catalyst E-603 and E-803 are also together listed in the table 4.
Example 5
This example is catalyzer thermostability contrast experiment.
Catalyzer c-1 of the present invention, c-2 and E-603, E-803 after 750 ℃ of pyroprocessing, are measured platinum crystal grain median size size in the catalyzer with JEM2000FX-II Electronic Speculum, the results are shown in table 5.Data show in the table, and through the thermal treatment of the same terms, catalyzer platinum crystal grain of the present invention is little, has high temperature sintering resistant performance preferably.
Example 6
This example is the little anti-evaluation result of catalyzer of the present invention and comparative catalyst c-4.
The micro anti-evaluation condition is: 500 ℃, 0.98MPa, hydrogen/oil mol ratio are 7, and the liquid air speed is 6 o'clock-1.Used reaction raw materials is that normal heptane is represented the catalyzer arenes selectivity with benzene in the reaction product and toluene productive rate, and transformation efficiency is represented the gross activity of catalyzer, and evaluation result is listed in table 6, and the result shows that catalyzer c-2 of the present invention, c-3 have higher arenes selectivity
Example 7
This example is catalyzer of the present invention and the evaluation result of comparative catalyst on middle-scale device.
Estimate and see Table 7 with stock oil character, evaluation result is listed in table 8.
Each elementary reaction condition is as follows in the table
Just live: 510 ℃ of 0.98MPa hydrogen to oil volume ratio 1000: 1
During volume space velocity 2.0
-1
Accelerated aging 530 ℃ of 0.69MPa hydrogen to oil volume ratio 500: 1
During volume space velocity 2.0
-1
Recover: 520 ℃ of 0.98MPa hydrogen to oil volume ratio 1000: 1
During volume space velocity 2.0
-1
As shown in Table 8, catalyzer of the present invention is compared with contrast medium, and initial activity is suitable, through than under the severe condition accelerate the aging step after, catalyzer c-2 of the present invention compares with the comparative catalyst.Virtue produces high 2.3 heavy %, transformation efficiency high 5.4 heavy %, and coke content is low about 20%, illustrate that catalyzer of the present invention has higher activity and arenes selectivity reaches stronger anti-carbon deposition ability.
Table 1
| Sequence number | Bearer number | Used each material formula of extrusion *, gram | ||||
| The sesbania powder | Nitric acid | Acetate | Citric acid | Water | ||
| Example 1 | a-1 | 2.0 | 0.9 | 2.6 | 4 | 70 |
| Example 2 | a-2 | 1.0 | 0.7 | 2.2 | 4 | 70 |
| Comparative Examples 1 | b-1 | 1.0 | 3.2 | - | 4 | 75 |
| Comparative Examples 2 | b-2 | 0.5 | 3.2 | - | - | 75 |
| Comparative Examples 3 | b-3 | 0.5 | - | 3.2 | - | 75 |
| Comparative Examples 4 | b-4 | 0.5 | 2.0 | 2.0 | - | 75 |
| Comparative Examples 5 | b-5 | 2.0 | - | 3.2 | 2.0 | 75 |
| Comparative Examples 6 | b-6 | 2.0 | - | - | 7.0 | 80 |
(
*The amount of each routine SB dry glue powder of lifting is 100 grams)
Table 2
| Sample number into spectrum | Crushing strength, newton/centimetre |
| a-1 | 140 |
| a-2 | 134 |
| b-1 | 53 |
| b-2 | 64 |
| b-3 | 65 |
| b-4 | 42 |
| b-5 | 86 |
| b-6 | 53 |
| E-603 | 66 |
| E-803 | 66 |
Table 3
| Sample number into spectrum | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | Pore radius distributes, body % | |||
| ＜30A | 30-50A | 50-100A | ＞100A | |||
| a-1 | 203 | 0.48 | 13.6 | 84.7 | 1.0 | 0.7 |
| a-2 | 201 | 0.46 | 14.3 | 84.4 | 1.2 | 0.1 |
| b-1 | 184 | 0.43 | 13.1 | 82.7 | 3.6 | 0.6 |
| b-2 | 209 | 0.41 | 47.9 | 50.1 | 1.5 | 0.5 |
| b-4 | 195 | 0.41 | 26.6 | 70.9 | 2.4 | 0.1 |
| E-803 | 184 | 0.45 | 19.6 | 77.3 | 2.4 | 0.7 |
Table 4
| Catalyzer | Carrier | Catalyzer is formed, heavy % | ||
| Pt | Re | Cl | ||
| c-1 | a-1 | 0.24 | 0.26 | 1.49 |
| c-2 | a-1 | 0.21 | 0.42 | 1.31 |
| c-3 | a-2 | 0.20 | 0.42 | 1.29 |
| c-4 | b-2 | 0.21 | 0.43 | 1.39 |
| E-603 | - | 0.30 | 0.30 | - |
| E-803 | - | 0.22 | 0.42 | - |
Table 5
| Catalyzer | c-1 | c-2 | E-603 | E-803 |
| The platinum average crystal grain, nanometer | 2.6 | 4.0 | 22.1 | 23.7 |
Table 6
Table 7
| Boiling range, ℃ | Hydrocarbon composition, heavy % | ||
| Fore-running 10%50%90% is done | Alkane | Naphthenic hydrocarbon | Aromatic hydrocarbons |
| 85 92 103 126 125 | 54.78 | 40.68 | 4.54 |
Table 8
Claims (5)
1, a kind of preparation method of platinum-rhenium reforming catalyst, be with aluminium hydrate powder with account for the sesbania powder mixing of aluminium hydrate powder weight 0.1-4.0%, be peptizing agent with mineral acid or organic acid, pinch through mixing, extrusion, drying, a 450-800 ℃ roasting make γ-Al
2O
3Carrier, load accounts for the platinum of butt alumina weight 0.1-0.8%, the rhenium of 0.1-1.5% and the chlorine of 0.5-2.0% again, it is characterized in that mixing used peptizing agent when pinching and be the mixed solution that the citric acid of the acetate of the nitric acid that accounts for aluminium hydrate powder weight 0.1-5.0%, 1.0-10.0% and 2.0-10.0% is formed.
2, in accordance with the method for claim 1, it is characterized in that used peptizing agent is the mixed solution that the citric acid of the acetate of the nitric acid that accounts for aluminium hydrate powder weight 0.5-1.5%, 2.0-4.0% and 3.0-6.0% is formed.
3, according to claim 1 or 2 described methods, it is characterized in that the high purity aluminium hydroxide that described aluminium hydrate powder gets for the aluminum alkoxide hydrolysis.
4, in accordance with the method for claim 1, it is characterized in that γ-Al of making
2O
3Load accounts for the platinum of butt alumina weight 0.2-0.4%, the rhenium of 0.2-0.8% and the chlorine of 0.8-1.5% on the carrier.
5, in accordance with the method for claim 1, the maturing temperature that it is characterized in that the aluminium hydroxide forming composition is 550-650 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96103410A CN1044377C (en) | 1996-03-21 | 1996-03-21 | Preparation of reforming platinum-rhenium catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96103410A CN1044377C (en) | 1996-03-21 | 1996-03-21 | Preparation of reforming platinum-rhenium catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1160747A CN1160747A (en) | 1997-10-01 |
| CN1044377C true CN1044377C (en) | 1999-07-28 |
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|---|---|---|---|
| CN96103410A Expired - Lifetime CN1044377C (en) | 1996-03-21 | 1996-03-21 | Preparation of reforming platinum-rhenium catalyst |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293208B (en) * | 2007-04-28 | 2010-10-20 | 中国石油化工股份有限公司 | Reforming catalyst and preparation method thereof |
| CN101293662B (en) * | 2007-04-28 | 2011-03-30 | 中国石油化工股份有限公司石油化工科学研究院 | Method for preparing gamma-aluminum oxide |
| CN102861618B (en) * | 2011-07-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of alumina supporter |
| CN103212369B (en) * | 2012-01-19 | 2016-09-14 | 北京三聚环保新材料股份有限公司 | A kind of high-strength FeOOH desulfurizer of room temperature desulfurization and preparation method thereof |
| CN106622304B (en) * | 2015-11-02 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of catalyst for reforming naphtha, preparation method and application |
| CN106622306B (en) * | 2015-11-02 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of reformation hydrogen hydrogenolysis catalyst, preparation method and application |
| 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 |
| CN108636405B (en) * | 2018-05-10 | 2021-02-02 | 天津大学 | Preparation method of high-selectivity diatomic catalyst for catalytic reforming |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4178268A (en) * | 1977-05-09 | 1979-12-11 | Uop Inc. | Selectively sulfided acidic multimetallic catalytic composite |
| CN1032951A (en) * | 1987-11-04 | 1989-05-17 | 中国石油化工总公司石油化工科学研究院 | A kind of catalyst for reforming naphtha |
| CN1056514A (en) * | 1990-05-11 | 1991-11-27 | 中国石油化工总公司化工科学研究院 | Catalyst for hydrogenation treatment of heavy fraction oil |
-
1996
- 1996-03-21 CN CN96103410A patent/CN1044377C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4178268A (en) * | 1977-05-09 | 1979-12-11 | Uop Inc. | Selectively sulfided acidic multimetallic catalytic composite |
| CN1032951A (en) * | 1987-11-04 | 1989-05-17 | 中国石油化工总公司石油化工科学研究院 | A kind of catalyst for reforming naphtha |
| CN1056514A (en) * | 1990-05-11 | 1991-11-27 | 中国石油化工总公司化工科学研究院 | Catalyst for hydrogenation treatment of heavy fraction oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1160747A (en) | 1997-10-01 |
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