CN1766046A - Hydrocarbons reforming catalyst and its preparation method - Google Patents
Hydrocarbons reforming catalyst and its preparation method Download PDFInfo
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- CN1766046A CN1766046A CN 200410086228 CN200410086228A CN1766046A CN 1766046 A CN1766046 A CN 1766046A CN 200410086228 CN200410086228 CN 200410086228 CN 200410086228 A CN200410086228 A CN 200410086228A CN 1766046 A CN1766046 A CN 1766046A
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Abstract
Disclosed is a hydrocarbons reforming catalyst which comprises compound carrier and the following active components (content calculated based on compound carrier): 0.01-2.0 wt% of group VIII metals, 0.01-3.0 wt% of group VIIB metals, and 0.1-10.0 wt% of halogens, the compound carrier comprises 70-99.5 wt% of aluminium oxide and 0.5-30 wt% of magnesium-aluminium hydrotalcite.
Description
Technical field
The present invention is a kind of hydrocarbons reforming catalyst and preparation method.Specifically, be a kind of dual metal reforming catalyst and preparation method who loads on the complex carrier.
Background technology
Catalytic reforming is the significant process of production high octane gasoline component and aromatic hydrocarbons, simultaneously the cheap hydrogen of by-product.In recent years, along with society constantly rises to the demand of reformate, the throughput of world's catalytic reforming unit increases year by year, and wherein semi regenerative reformer occupies significant proportion.
At present, half generative reforming catalyzer is mainly platinum-rhenium catalyst, and support of the catalyst is mainly single aluminum oxide.Alumina supporter is because its pore structure that is fit to and stable crystalline phase are widely used in reforming catalyst.Reforming catalyst is to have the metal function of hydrogenation/dehydrogenation and the dual-function catalyst of isomerization acid function, and the two is coordinated in the reforming process of hydro carbons mutually.Aluminum oxide in reforming catalyst as the carrier of bigger serface, can the dispersed metal active component, improve the utilization ratio of metal active constituent element, prevent the sintering of metal active constituent element.In addition, alumina supporter can provide reforming reaction needed acid function, and by adjusting the acid function of the cl content adjustment catalyzer on the catalyzer.
Because traditional platinum-rhenium reforming catalyst is dual-function reforming catalyst, to the modification of catalyzer mainly from carrying out aspect metal active constituent element and the carrier two.Aspect the metal active constituent element, reach the purpose at modulation metal active center by modification to main metal constituent element, thus the activity of regulating catalyst, selectivity and stability.Aspect carrier, the specific surface area by changing carrier, pore structure and acid performance of coming regulating catalyst.Discover that the PtKL zeolite has the aromatization activity higher than traditional reforming catalyst to hydrocarbon reformation.On reaction mechanism, the PtKL zeolite is different from traditional with Al fully
2O
3Be the dual-function catalyst of carrier, but alkaline mechanism.Because its high aromatization activity never stops in the research aspect the reformation the PtKL zeolite.But such catalyzer does not still solve it to the susceptibility of sulphur and relatively poor stability so far.The research of this respect inspires people whether can seek other similar basic supports and is applied to reforming catalyst.Magnesium aluminum-hydrotalcite is a kind of similar basic supports.USP5276233 uses with carbonate, and to be the anionic magnesium aluminum-hydrotalcite that contains precious metal carry out the aromatization of hydro carbons as catalyzer, and arenes selectivity is higher.USP5245096 is that carrier loaded VIII family metal prepares catalyzer with hydrotalcite, and wherein the divalent cation in the hydrotalcite is selected from copper, magnesium, manganese, zinc and VIII family metal, and Tricationic is selected from aluminium, chromium or iron.Such catalyzer is used for the catalytic conversion reaction of normal hexane, wherein is that the catalyzer of carrier demonstrates higher transformation efficiency and arenes selectivity with the magnesium aluminum-hydrotalcite.
Summary of the invention
The purpose of this invention is to provide a kind of dual metal reforming catalyst and preparation method thereof, reaction has good aromatization activity, selectivity and activity stability to this catalyzer to hydrocarbon reformation.
Hydrocarbons reforming catalyst provided by the invention, comprise complex carrier and be the following active ingredient of content of calculating benchmark with the complex carrier: the VIII family metal of 0.01～2.0 quality %, the VIIB family metal of 0.01～3.0 quality % and the halogen of 0.1～10.0 quality %, described complex carrier is made up of the aluminum oxide of 70～99.5 quality % and the magnesium aluminum-hydrotalcite of 0.5～30 quality %.
The present invention forms complex carrier with aluminum oxide and magnesium aluminum-hydrotalcite, again precious metal and VIIB family metal load are made catalyzer on carrier, because the magnesium aluminum-hydrotalcite in the carrier is alkalescence, with be the tart aluminum oxide and interact, can improve the catalyst acid sexual function, when making catalyzer be used for the hydrocarbon reformation reaction, C
1～C
4The lower carbon number hydrocarbons productive rate reduce, aromatics yield improves.
Embodiment
Catalyzer of the present invention adopts the complex carrier of being made up of aluminum oxide and magnesium aluminum-hydrotalcite, and metal active constituent is VIII family metal and VIIB family metal, improves the performance of catalyzer by the content of magnesium aluminum-hydrotalcite in the control complex carrier.
Described magnesium aluminum-hydrotalcite can be natural anionic clay, also can be the product of synthetic, and it forms general formula is Mg
1-xAl
x(OH)
2(A
N-)
X/nMH
2O, in the formula, x=0.2～0.33, A
N-Be selected from CO
3 2-, NO
3 -Or Cl
-, n is 1 or 2, m=1～10.Magnesium aluminum-hydrotalcite has the crystalline texture that is similar to layered clay mineral, and its basic structure layer is formed by Mg-OH, Al-OH are octahedra, forms positively charged laminate, between structural sheet filling anion layer and water molecules.The preferred CO of the negatively charged ion of the magnesium aluminum-hydrotalcite that catalyzer of the present invention is selected for use
3 2-Or NO
3 -
Preferred 0.05～1.0 quality % of VIII family metal content, preferred 0.05～1.0 quality % of VIIB family metal content, preferred 0.5～3.0 quality % of content of halogen in the catalyzer of the present invention.
Preferred 5～30 quality % of the content of magnesium aluminum-hydrotalcite in the described complex carrier.The preferred gama-alumina of used aluminum oxide.The shape of carrier can be ball-type, stripe shape, sheet, particulate state or trifolium-shaped, preferred stripe shape or ball-type, more preferably stripe shape.
The preferred platinum of VIII family metal in the described catalyzer, the preferred rhenium of VIIB family metal, the preferred chlorine of halogen.
Preparation of catalysts method of the present invention comprises the steps:
(1) aluminum oxide and magnesium aluminum-hydrotalcite are mixed, kneading and compacting makes complex carrier after drying, the roasting,
(2) compound that will contain the compound of VIII family metal and contain VIIB family metal is made into steeping fluid, floods described complex carrier, will flood afterwards solid drying, the roasting of gained again.
(1) step is the preparation process of complex carrier in the described method, earlier aluminum oxide and magnesium aluminum-hydrotalcite is mixed during preparation, adopts any known ordinary method to carry out moulding again, as spin, extrusion, compressing tablet, and preferred extruded moulding.The method of extruded moulding is to add earlier suitable quantity of water to mix and pinch in above-mentioned mixed raw materials powder, and is easy for making extrusion, preferably adds peptizing agent and extrusion aid, extruded moulding then in material powder.The preferred sesbania powder of described extrusion aid, the mass ratio of extrusion aid and material powder is 0.01～0.30: 1, the preferred rare nitric acid of peptizing agent, citric acid, acetate or the mixture of both or three kinds arbitrarily in them, the mass ratio of described peptizing agent and material powder is 0.7～1.5: 1.Behind the extruded moulding, with extrudate 30～80 ℃ of dryings 4～24 hours, 100～150 ℃ of dryings 6～24 hours, 400～800 ℃ of roastings promptly made the stripe shape complex carrier in 2～24 hours.
Described method (2) step is introduced active ingredient for dipping, adopts pickling process, and preferred employing is soaked method altogether each metal component, halogen are introduced complex carrier.Steeping fluid is 0.4～2.0 with the liquid/solid volume ratio of carrier during dipping, when liquid/solid volume than being saturated dipping less than 1.0 the time, the steeping fluid suppressed by vector absorbs fully.The preferred liquid of saturated dipping/solid volume ratio is 0.4～0.8.When liquid/solid volume than being the supersaturation dipping greater than 1.0 the time, supersaturation is flooded remaining steeping fluid and need be removed, it is preferred that liquid/the solid volume ratio is 1.05～2.0.Above-mentioned suitable dipping temperature is 15～40 ℃, preferred 20～30 ℃.Dipping back gained solid drying, roasting promptly get catalyzer.Suitable drying temperature is 80～150 ℃, and maturing temperature is 400～800 ℃, preferred 400～600 ℃.
In the aforesaid method, the used compound that contains VIII family metal of preparation steeping fluid preferably contains platinic compound, and the compound that contains VIIB family metal preferably contains rhenium compound.The described platinic compound that contains is selected from Platinic chloride, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, Tetrachloroplatinum hydrate, dichloride two chloroformyl platinum, dinitrobenzene tetramino platinum or tetranitro sodium platinate, contains rhenium compound and is selected from perrhenic acid, ammonium perrhenate or potassium perrhenate.
For making metal component uniform distribution in carrier, generally in dipping solution, add competitive adsorbate.Preferred competitive adsorbate is HCl or trichoroacetic acid(TCA), and both can add steeping fluid respectively, also can add steeping fluid simultaneously.The concentration of competitive adsorbate in steeping fluid is counted 0.2～5.0 quality % with chlorine, preferred 0.8～3.0 quality %.If adding trichoroacetic acid(TCA) is competitive adsorbate, after the carrier drying, be preferably in 180～230 ℃ of heating 0.5～10 hour, in the steeping fluid so that trichoroacetic acid(TCA) desorption from carrier.
Catalyzer of the present invention must reduce and prevulcanized before use.The reducing gas that catalyst reduction is used can be hydrogen or carbon monoxide, preferred hydrogen.Preferred 400～500 ℃ of reduction temperature, gas during reduction/agent volume ratio preferred 500～1400: 1, preferred 4～8 hours of recovery time.Also need carry out prevulcanized after the catalyst reduction, prevulcanized is to add an amount of sulfide in reducing gas, preferred hydrogen sulfide, and it is 0.01～1.00% that the add-on of hydrogen sulfide should make sulphur content in the catalyzer (with respect to catalyst quality), preferred 0.04～1.0%.Described pre-curing temperature is 400～500 ℃.
Catalyzer of the present invention is suitable for the catalytic reforming reaction of hydro carbons.The described hydrocarbon raw material that is used to reform is the whole-distillate gasoline of 40～230 ℃ of boiling ranges, the mixture of forming as the gasoline of straight-run spirit or its admixture heat cracking or catalytic cracking, part reformed naphtha or dehydrogenation petroleum naphtha.
The catalytic reaction condition that catalyzer of the present invention is suitable for is: 0.1～10.0MPa, preferred 0.3～2.5MPa, and 370～600 ℃, preferred 450～550 ℃, hydrogen/hydrocarbon volume ratio 300～800: 1, preferred 400～600: 1, charging mass space velocity 0.1～20.0 o'clock
-1, preferred 0.5～5.0 o'clock
-1
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare catalysis profit of the present invention.
(1) preparation carrier
Get 200 gram aluminium hydrate powders (German Condea company produces, trade mark SB), 1.5 grams consist of Mg
4Al
2(OH)
12(NO
3)
24H
2The magnesium aluminum-hydrotalcite of O and 4.0 gram sesbania powder mix, be nitric acid, the 8.6 gram citric acids of 35.0 quality % again with 135.0 ml deionized water, 4 ml concns, 14 milliliters of acetate is made into 180 milliliters solution, add to mix in the above-mentioned mixed powder and pinch, extruded moulding then, 60 ℃ of dryings 24 hours, 120 ℃ of dryings 6 hours, 650 ℃ of roastings 6 hours obtain complex carrier.
(2) preparation catalyzer
Get the carrier of 60 gram (1) step preparations, the steeping fluid that is made into Platinic chloride, perrhenic acid and hydrochloric acid flooded 24 hours in 25 ℃, contain Pt 0.22%, Re 0.58%, Cl 1.8% quality of butt carrier (all with respect to) in the steeping fluid, the liquid of dipping/solid volume ratio is 1.9.The dipping after-filtration, 60 ℃ of dryings 24 hours, 120 ℃ of dryings 12 hours were roasting 4 hours under 700 the condition in 500 ℃, gas/agent volume ratio in dry air again, make catalyst B with the gained solid, its composition sees Table 1.
Example 2
Method according to example 1 prepares catalyzer C, and when different was (1) step preparation complex carrier, adding consisted of Mg
6Al
2(OH)
16CO
34H
2Magnesium aluminum-hydrotalcite 7.5 grams of O, the composition of catalyzer C sees Table 1.
Example 3
Method according to example 1 prepares catalyzer D, and when different was (1) step preparation complex carrier, adding consisted of Mg
6Al
2(OH)
16CO
34H
2Magnesium aluminum-hydrotalcite 22.5 grams of O, the composition of catalyzer D sees Table 1.
Example 4
Method according to example 1 prepares catalyzer E, and when different was (1) step preparation complex carrier, adding consisted of Mg
6Al
2(OH)
16CO
34H
2Magnesium aluminum-hydrotalcite 45 grams of O, the composition of catalyzer E sees Table 1.
Example 5
This example is a Comparative Examples.Method according to example 1 prepares catalyst A, and different does not add magnesium aluminum-hydrotalcite when being (1) step preparation carrier, and the composition of catalyst A sees Table 1.
Example 6
This example is a Comparative Examples.Method according to example 1 prepares catalyzer F, and different does not add aluminum oxide when being (1) step preparation carrier, and the composition of catalyzer F sees Table 1.
Example 7
This example is estimated catalyst performance of the present invention.
Loading catalyst on the micro anti-evaluation device is to use H under 500 the condition in 480 ℃, gas/agent volume ratio
2Reduced 4 hours, and added 0.10% (with respect to catalyst quality) hydrogen sulfide then in hydrogen stream, 425 ℃ are carried out prevulcanized to catalyzer.With the normal heptane is that raw material is estimated catalyzer of the present invention and comparative catalyst, and appreciation condition is: 500 ℃, when 0.69MPa, charging mass space velocity 2.0
-1, hydrogen/hydrocarbon volume ratio 500: 1,72 hours reaction times.Evaluation result sees Table 2.
As shown in Table 2, catalyst B～E of the present invention and single aluminum oxide are that the comparative catalyst A of carrier compares C in the reaction product
1～C
4Content is lower, and benzene and toluene (B+T) content is higher, illustrates that catalyzer of the present invention has good aromatization activity and arenes selectivity.And be the contrast medium F of carrier with the magnesium aluminum-hydrotalcite, active and aromatics yield is all very low at 6 hours afterreactions of reaction, and to react after 36 hours be basic inactivation, illustrates that its activity stability is relatively poor.
Table 1
| Instance number | The catalyzer numbering | Magnesium aluminum-hydrotalcite used in the carrier is formed | Carrier is formed, quality % | The catalyst activity component concentration, quality % | |||
| Al 2O 3 | Magnesium aluminum-hydrotalcite | Pt | Re | Cl | |||
| 1 | B | Mg 4Al 2(OH) 12(NO 3) 2·4H 2O | 99 | 1 | 0.22 | 0.44 | 1.10 |
| 2 | C | Mg 6Al 2(OH) 16CO 3·4H 2O | 95 | 5 | 0.21 | 0.46 | 1.08 |
| 3 | D | Mg 6Al 2(OH) 16CO 3·4H 2O | 85 | 15 | 0.22 | 0.46 | 1.06 |
| 4 | E | Mg 6Al 2(OH) 16CO 3·4H 2O | 70 | 30 | 0.21 | 0.45 | 1.12 |
| 5 | A | - | 100 | 0 | 0.21 | 0.45 | 1.11 |
| 6 | F | Mg 6Al 2(OH) 16CO 3·4H 2O | 0 | 100 | 0.64 | 0.74 | 0.21 |
Table 2
| Reaction times hr | C 1～C 4, quality % | B+T, quality % | ||||||||||
| B | C | D | E | A | F | B | C | D | E | A | F | |
| 6 | 38.37 | 39.42 | 33.79 | 33.44 | 37.89 | 28.03 | 37.94 | 38.09 | 38.65 | 38.70 | 36.06 | 14.19 |
| 12 | 37.14 | 35.03 | 33.03 | 32.80 | 36.78 | 17.39 | 38.58 | 38.79 | 38.38 | 38.40 | 36.13 | 7.21 |
| 18 | 35.8 | 33.96 | 32.34 | 32.14 | 35.64 | 15.89 | 38.38 | 38.70 | 38.51 | 38.37 | 35.39 | 5.83 |
| 24 | 34.57 | 34.68 | 31.45 | 31.60 | 36.21 | 14.88 | 37.49 | 38.77 | 38.44 | 38.03 | 33.79 | 5.06 |
| 30 | 32.38 | 32.97 | 31.42 | 30.89 | 33.68 | 13.44 | 36.72 | 37.68 | 37.76 | 37.70 | 34.96 | 4.12 |
| 36 | 32.11 | 32.24 | 30.57 | 30.57 | 33.58 | 12.89 | 35.43 | 37.33 | 37.36 | 37.48 | 34.47 | 3.73 |
| 42 | 32.10 | 31.10 | 30.00 | 30.09 | 33.41 | 35.23 | 37.37 | 36.82 | 37.10 | 34.09 | ||
| 48 | 31.55 | 30.41 | 29.27 | 29.43 | 33.42 | 35.24 | 36.90 | 37.06 | 36.77 | 32.96 | ||
| 54 | 30.87 | 29.84 | 28.78 | 28.69 | 33.00 | 34.26 | 36.29 | 36.08 | 36.40 | 32.67 | ||
| 60 | 30.45 | 29.44 | 28.06 | 28.21 | 32.17 | 33.33 | 35.57 | 36.01 | 36.23 | 32.59 | ||
| 66 | 29.54 | 28.94 | 27.32 | 27.32 | 31.38 | 33.17 | 34.49 | 35.78 | 36.00 | 32.11 | ||
| 72 | 28.63 | 27.94 | 26.54 | 26.87 | 31.64 | 33.00 | 34.70 | 35.56 | 35.67 | 31.12 | ||
| 76 | 28.25 | 27.81 | 26.77 | 26.54 | 30.80 | 32.85 | 33.76 | 35.02 | 35.40 | 30.95 | ||
Claims (10)
1, a kind of hydrocarbons reforming catalyst, comprise complex carrier and be the following active ingredient of content of calculating benchmark with the complex carrier: the VIII family metal of 0.01～2.0 quality %, the VIIB family metal of 0.01～3.0 quality % and the halogen of 0.1～10.0 quality %, described complex carrier is made up of the aluminum oxide of 70～99.5 quality % and the magnesium aluminum-hydrotalcite of 0.5～30 quality %.
2, according to the described catalyzer of claim 1, the content that it is characterized in that magnesium aluminum-hydrotalcite in the described complex carrier is 5～30 quality %.
3,, it is characterized in that VIII family metal content is that 0.05～1.0 quality %, VIIB family metal content are that 0.05～1.0 quality %, content of halogen are 0.5～3.0 quality % in the described catalyzer according to the described catalyzer of claim 1.
4, according to the described catalyzer of claim 1, it is characterized in that described VIII family metal is selected from platinum, VIIB family metal is selected from rhenium, halogen is a chlorine.
5, according to the described catalyzer of claim 1, the composition general formula that it is characterized in that described magnesium aluminum-hydrotalcite is Mg
1-XAl
X(OH)
2(A
N-)
X/nMH
2O, in the formula, x=0.2～0.33, A
N-Be selected from CO
3 2-, NO
3 -Or Cl
-, n is 1 or 2, m=1～10.
6,, it is characterized in that described aluminum oxide is a gama-alumina according to the described catalyzer of claim 1.
7, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) aluminum oxide and magnesium aluminum-hydrotalcite are mixed, kneading and compacting makes complex carrier after drying, the roasting,
(2) compound that will contain the compound of VIII family metal and contain VIIB family metal is made into steeping fluid, floods described complex carrier, will flood afterwards solid drying, the roasting of gained again.
8, in accordance with the method for claim 7, it is characterized in that the steeping fluid described in (2) step and the liquid/solid volume ratio of complex carrier are 0.4～2.0: 1.
9, in accordance with the method for claim 7, the compound that it is characterized in that containing VIII family metal is for containing platinic compound, and the compound that contains VIIB family metal is for containing rhenium compound.
10, in accordance with the method for claim 9, it is characterized in that the described platinic compound that contains is selected from Platinic chloride, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, Tetrachloroplatinum hydrate, dichloride two chloroformyl platinum, dinitrobenzene tetramino platinum or tetranitro sodium platinate, contains rhenium compound and is selected from perrhenic acid, ammonium perrhenate or potassium perrhenate.
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|---|---|---|---|
| CNB2004100862283A CN100478072C (en) | 2004-10-28 | 2004-10-28 | Hydrocarbons reforming catalyst and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100862283A CN100478072C (en) | 2004-10-28 | 2004-10-28 | Hydrocarbons reforming catalyst and its preparation method |
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| Publication Number | Publication Date |
|---|---|
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| CN100478072C CN100478072C (en) | 2009-04-15 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081362B (en) * | 2006-05-31 | 2010-09-08 | 中国石油化工股份有限公司 | Carrier containing magnalium complexes and method for preparing the same |
| EP2331488A4 (en) * | 2008-09-04 | 2012-10-24 | Lummus Technology Inc | Olefin isomerization and metathesis catalyst |
-
2004
- 2004-10-28 CN CNB2004100862283A patent/CN100478072C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081362B (en) * | 2006-05-31 | 2010-09-08 | 中国石油化工股份有限公司 | Carrier containing magnalium complexes and method for preparing the same |
| EP2331488A4 (en) * | 2008-09-04 | 2012-10-24 | Lummus Technology Inc | Olefin isomerization and metathesis catalyst |
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| Publication number | Publication date |
|---|---|
| CN100478072C (en) | 2009-04-15 |
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