CN1782029A - Reforming catalyst for hydrocarbon and preparing method - Google Patents
Reforming catalyst for hydrocarbon and preparing method Download PDFInfo
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- CN1782029A CN1782029A CN 200410096313 CN200410096313A CN1782029A CN 1782029 A CN1782029 A CN 1782029A CN 200410096313 CN200410096313 CN 200410096313 CN 200410096313 A CN200410096313 A CN 200410096313A CN 1782029 A CN1782029 A CN 1782029A
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Abstract
The hydrocarbon reforming catalyst includes carrier and the active components including VIII metal in 0.01-2.0 (in wt% of the carrier, the same below), VIIB metal 0.01-5.0 and halogen 0.1-10.0. The carrier consists of alumina in 80-99 wt% and amorphous silica-alumina in 1-20 wt%. The catalyst is used in naphtha reforming reaction and can raise the yield of liquefied gas in gas product while maintaining the liquid yield and arene yield.
Description
Technical field
The present invention is a kind of hydrocarbons reforming catalyst and preparation method, specifically, is a kind of reforming catalyst and preparation method who contains bimetal active ingredient and complex carrier.
Background technology
Catalytic reforming is to take the naphtha fraction as raw material production stop bracket gasoline mediation component and aromatic hydrocarbons, the significant process of by-product hydrogen simultaneously.
The main purpose product of catalytic reforming is a liquid product, and production process liquid product yield height is the sign of catalyst selectivity quality normally.But in some areas, liquefied gas has very big commercial market.Because the increasingly stringent of environmental requirement, very big potential market is arranged as the no sulphur liquefied gas of environment-friendly type urban public transport carrier vehicle clean fuel.Thereby in catforming process, do not reducing or reducing less on the basis of liquid product yield, reduce the dry gas yied in the gaseous product, improve liquefied gas yield and can produce better economic benefit.
Reforming catalyst is the core of catalytic reforming technology.Reforming catalyst is a kind of dual-function catalyst, comprises the metal function of isomerization acid function and hydrogenation/dehydrogenation, and two kinds of functions are mated in the hydrocarbon reformation process mutually, and indispensable, the modulation of these two kinds of functions and improvement are the reforming catalyst research emphasis.According to the production purpose of catalytic reforming,, be the means of adjusting products distribution to the modulation that carries out of catalyst acid sexual function and metal function.
Add in support of the catalyst that to have the tart molecular sieve be to improve one of reforming catalyst tart method, all in alumina supporter, add the acidity that mordenite strengthens catalyzer as USP3511773 and USP3679575.CN1384176A then adds the performance that metal-modified mordenite and/or β zeolite improve catalyzer in aluminum oxide.The characteristics of these catalyzer are that acid function is strong, cracking performance is strong, gas recovery ratio is high, but yield of liquefied gas wherein is not high.
Summary of the invention
The purpose of this invention is to provide a kind of hydrocarbons reforming catalyst and preparation method, this catalyzer can improve the ratio of liquefied gas in the gaseous product under the constant substantially situation of aromatic hydrocarbons and liquid yield.
Hydrocarbons reforming catalyst provided by the invention, comprise carrier and be the following active ingredient of content of calculating benchmark with the carrier: VIII family metal 0.01～2.0 quality %, VIIB family metal 0.01～5.0 quality %, halogen 0.1～10.0 quality %, described carrier is made up of the aluminum oxide of 80～99 quality % and the amorphous aluminum silicide of 1～20 quality %.
The present invention comes the modulation support acidity by introduce an amount of amorphous aluminum silicide in carrier, the reforming catalyst of gained after the loaded metal active ingredient, reforming reaction is received under the situation that keeps suitable numerical value at aromatics yield and liquid, improved the content of liquefied gas in the gaseous product.
Embodiment
Amorphous aluminum silicide is a kind of acid solid matter with bigger specific surface and pore volume, and its acidity is strong than aluminum oxide, and an amount of amorphous aluminum silicide that adds can be adjusted its acidity in alumina supporter, suitably increases the liquefied gas ratio in the reformed gas product.
Preferred 0.05～1.0 quality % of VIII family metal content in the catalyzer of the present invention, preferred 0.05～2.0 quality % of VIIB family metal content, preferred 0.1～3.0 quality % of content of halogen.Preferred 5～15 quality % of the content of amorphous aluminum silicide in the described carrier, the silica alumina ratio of amorphous aluminum silicide, promptly the mol ratio of silicon oxide and aluminum oxide preferred 0.8～1.6: 1.
VIII family metal is selected from ruthenium, rhodium, palladium, platinum, iridium or palladium in the described catalyzer, preferred platinum or palladium, more preferably platinum, the preferred rhenium of VIIB family metal, the preferred chlorine of halogen.
The shape of catalyzer can be ball-type, excellent type, ball, bead, sheet, granular, trifolium-shaped or stripe shape, preferred stripe shape.
Preparation of catalysts method provided by the invention, comprise amorphous aluminum silicide and aluminium hydrate powder are mixed aftershaping, obtain carrier after drying, the roasting, adopt step impregnation then or be total to the method for flooding and in described carrier, introduce VIII family metal and VIIB family metal.
Described amorphous aluminum silicide is introduced in the carrier moulding process, and preferred forming method is an extruded moulding.Concrete operation method is: amorphous aluminum silicide and aluminium hydrate powder are mixed, add the mixed even back extrusion of pinching of suitable quantity of water, extrusion aid and peptizing agent, obtain containing the complex carrier of amorphous aluminum silicide after the strip drying of extruding, the roasting.The mass ratio of extrusion aid and aluminium hydrate powder is 0.05～0.30: 1 during extrusion, and the mass ratio of peptizing agent and aluminium hydrate powder is 0.9～1.5: 1.Described extrusion aid is selected from the sesbania powder, and peptizing agent is selected from rare nitric acid, citric acid, acetate, hydrochloric acid or they both mixtures or the mixture of three kinds of acid arbitrarily, and the concentration of nitric acid should be 0.5～10.0 quality % in the peptizing agent of preparation.
The present invention adopts conventional pickling process to introduce active ingredient in carrier to prepare catalyzer.Dipping can adopt and soak method altogether or branch soaks method, and the preferred employing method of soaking is altogether introduced active ingredient.Earlier be mixed with steeping fluid with compound that contains VIII family metal and the compound that contains VIIB family metal during dipping, the amount of each constituent element that contains in the steeping fluid should make the amount of this constituent element in the finished product reach the prescribed value of catalyzer.With the steeping fluid impregnated carrier of preparation, liquid-solid volume ratio is 1.0～2.0: 1 during dipping then.Comparatively Shi Yi dipping temperature is 15～40 ℃, preferred 20～30 ℃.After finishing, dipping will promptly get catalyzer after gained solid drying, the roasting.
The compound of the used VIII of dipping family metal is the water-soluble platinic compound that contains in the aforesaid method, and the compound of VIIB family metal is for containing rhenium compound.
The described water-soluble platinic compound that contains is selected from Platinic chloride, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, Tetrachloroplatinum hydrate, two chloroformyl platinum, dinitrobenzene diamino platinum, tetranitro sodium platinate, preferred Platinic chloride or ammonium chloroplatinate.Contain rhenium compound and be selected from perrhenic acid, ammonium perrhenate or potassium perrhenate, preferred perrhenic acid or ammonium perrhenate.
In order to make halogen and metal component uniform distribution in carrier, need in dipping solution, to add competitive adsorbate.Competitive adsorbate can be organic acid or mineral acid, is preferably HCl or trichoroacetic acid(TCA), and both can add steeping fluid separately, also can add steeping fluid simultaneously.If when adding steeping fluid simultaneously, the mass ratio of HCl and trichoroacetic acid(TCA) is 0.01～100: 1, preferred 0.1～10: 1.The concentration of described 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, is preferably in 180～230 ℃ and handled 0.5～10 hour, in the steeping fluid so that the trichoroacetic acid(TCA) desorption.
In the process of above-mentioned Preparation of Catalyst, described drying temperature is 30～150 ℃, and is preferred earlier 30～80 ℃ of dryings 4～24 hours, and then 100～150 ℃ of dryings 6～24 hours.Described maturing temperature is 450～800 ℃, and preferred 550～650 ℃, roasting time is 2～24 hours, preferred 2～8 hours.
In order to regulate chlorine contained in the catalyzer, can in the catalyzer roasting process, add certain amount of H Cl and water vapor and carry out the processing of water chlorine.Water chlorine treatment process be with oxidized catalyst in air, in 400～600 ℃, H
2Handled 0.5～5.0 hour under the condition of O/HCl mol ratio 1.0～150: 1.If adopt step impregnation method, then water chlorine is handled the last time and is carried out behind the impregnated carrier.
The catalyzer that makes after the roasting need reduce and prevulcanized before use.Reduction and prevulcanized are all carried out in hydrogen atmosphere.Reduction temperature is 470～500 ℃, and the time is 2～8 hours; Pre-curing temperature is 370～420 ℃, and the time is 2～8 hours.In the hydrogen stream that feeds catalyzer, add an amount of sulfide during prevulcanized and get final product the preferred hydrogen sulfide of described sulfide.
Catalyzer of the present invention is applicable to that boiling range is the catforming process of the gasoline component of the described boiling range that produces of 40～230 ℃ virgin naphtha or its blending secondary processing process, and described secondary processing process comprises catalytic cracking, hydrocracking, delayed coking etc.
The processing condition that catalyzer of the present invention is suitable for are pressure 0.1～10.0MPa, preferred 0.3～2.5MPa, 370～600 ℃ of temperature, preferred 450～550 ℃, hydrogen/hydrocarbon volume ratio 600～2000: 1, preferred 800～1500: 1 feeding liquid hourly space velocity (LHSV) 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
Prepare catalyzer of the present invention.
(1) preparation contains the carrier of amorphous aluminum silicide.
Get 100 gram SB aluminium hydrate powders (productions of South Africa Sasol company), 4 gram sial (mole) than being that 1.2 amorphous aluminum silicide (production of South Africa Sasol company) and 2 restrains the sesbania powder and mixes, again 10 gram citric acids, 3 milliliters of salpeter solutions of 1: 1,10 milliliter 36% acetic acid solution and 90 ml deionized water wiring solution-formings are added in the above-mentioned solid that mixes, fully mix and pinch the back extruded moulding.60 ℃ of dryings 6 hours, 120 ℃ of dryings 12 hours, 650 ℃ of roastings obtained containing the alumina supporter of amorphous aluminum silicide 5 quality % in 4 hours.
(2) preparation catalyzer
Get above-mentioned bar shaped carrier, be made into steeping fluid, make to contain Pt 0.22%, Re 0.58%, Cl 1.8% (all with respect to the carrier quality) in the steeping fluid with a certain amount of Platinic chloride, perrhenic acid and hydrochloric acid.25 ℃ of impregnated carriers 24 hours, liquid/solid volume ratio was 1.9 with described steeping fluid.The dipping after-filtration, in 60 ℃ of dryings 24 hours, 120 ℃ of dryings 12 hours were roasting 4 hours under 700: 1 the condition in 500 ℃, gas/agent volume ratio in air then with the gained solid, 480 ℃, gas/agent volume ratio are to use H under 500: 1 the condition
2Reduced 4 hours, and obtained catalyst B, its composition sees Table 1.
Example 2
Method by example 1 prepares catalyzer, and different is that added amorphous aluminum silicide of (1) step is 8 grams, and the composition of the catalyzer C that makes sees Table 1.
Example 3
Method by example 1 prepares catalyzer, and different is that added amorphous aluminum silicide of (1) step is 12 grams, and the composition of the catalyzer D that makes sees Table 1.
Example 4
Method by example 1 prepares catalyzer, and different is that added amorphous aluminum silicide of (1) step is 16 grams, and the composition of the catalyzer E that makes sees Table 1.
Comparative Examples 1
Press the method for USP3679575, preparation contains the alumina supporter of mordenite 5 quality %, and the method by 1 (2) step of example prepares catalyzer F then, and its composition sees Table 1.
Comparative Examples 2
Method by example 1 prepares the comparative catalyst, and different is not add amorphous aluminum silicide in the preparing carriers process, and the composition of the catalyst A of preparation sees Table 1.
Example 5
This example is estimated catalyzer of the present invention and comparative catalyst's reactivity worth.
Loading catalyst on 1 milliliter of micro-reactor, the hydrogen sulfide that adds 0.10% (catalyst quality relatively) in 425 ℃ hydrogen carries out prevulcanized to catalyzer, obtains the sulphided state catalyzer of the about 0.07 quality % of sulfur-bearing.
With the analytical pure normal heptane was raw material, 1.0MPa, 500 ℃, feed volume air speed 6.0 hours
-1, react under hydrogen/condition of 1200: 1 of hydrocarbon volume ratio, reaction result sees Table 2.
As shown in Table 2, catalyst B～E of the present invention and aluminum oxide are that the comparative catalyst A of carrier compares, at aromatic hydrocarbons (benzene+toluene) productive rate, total gas (C
1～C
4) under the close situation of productive rate, liquefied gas (C in the gaseous product
3+ C
4) productive rate higher.Though and the liquefied gas yield of comparative catalyst F is higher, dry gas (C in the gaseous product
1+ C
2) productive rate obviously increases, aromatics yield obviously descends.
Example 6
Loading catalyst on 10 milliliters of devices carries out presulfiding of catalyst by the method for example 5 earlier, is that raw material compares evaluation to catalyzer with refining petroleum naphtha then, and the raw material composition sees Table 3.Appreciation condition is: 0.8MPa, 500 ℃, charging air speed 2.0 hours
-1, hydrogen/oil volume is than 800: 1.Evaluation result sees Table 4.
As shown in Table 4, catalyst B～E of the present invention compares with comparative catalyst A, under the approaching situation of liquid yield and aromaticity content, generates the liquefied gas (C in the gas
3+ C
4) and dry gas (C
1+ C
2) the volume ratio raising, illustrate that the liquefied gas content in the gas increases.And the liquid of comparative catalyst F is received and virtue contain all lower, the liquefied gas (C in the generation gas
3+ C
4) and dry gas (C
1+ C
2) volume ratio lower, illustrate that the gaseous product that increases mainly is a dry gas.
Table 1
| Instance number | The catalyzer numbering | Carrier is formed, quality % | Catalyst component content, quality % | ||||
| Amorphous aluminum silicide | Aluminum oxide | Mordenite | Pt | Re | Cl | ||
| 1 | B | 5.1 | 94.9 | - | 0.22 | 0.46 | 1.18 |
| 2 | C | 9.6 | 90.4 | - | 0.22 | 0.46 | 1.21 |
| 3 | D | 13.8 | 86.2 | - | 0.22 | 0.46 | 1.21 |
| 4 | E | 17.6 | 82.4 | - | 0.22 | 0.46 | 1.18 |
| Comparative Examples 1 | F | - | 95 | 5 | 0.22 | 0.46 | 1.16 |
| Comparative Examples 2 | A | - | 100 | - | 0.22 | 0.46 | 1.20 |
Table 2
| The catalyzer numbering | C 1+C 2, quality % | C 3+C 4, quality % | C 1～C 4, quality % | Benzene+toluene, quality % |
| B | 5.13 | 28.12 | 33.25 | 26.24 |
| C | 5.09 | 29.24 | 34.33 | 25.98 |
| D | 5.49 | 33.61 | 39.10 | 25.34 |
| E | 5.45 | 34.21 | 39.66 | 25.16 |
| A | 10.83 | 22.35 | 33.18 | 26.70 |
| F | 17.11 | 28.25 | 45.36 | 19.98 |
Table 3
| Component concentration, quality % | Alkane | Naphthenic hydrocarbon | Aromatic hydrocarbons | Virtue is dived |
| C 3 C 4 C 5 C 6 C 7 C 8 C 9 C 10 | 0.05 0.06 1.52 11.45 21.92 16.13 5.97 0.42 | 0.76 8.07 14.12 12.38 4.22 0.12 | 0.42 0.88 1.42 0.09 | 7.91 14.14 13.14 4.11 0.11 |
| Amount to quality % | 57.52 | 39.67 | 2.81 | 39.41 |
Table 4
| The catalyzer numbering | (C 3+C 4)/(C 1+C 2) volume ratio | Liquid yield, quality % | Aromaticity content, quality % |
| B | 0.50 | 82.1 | 70.12 |
| C | 0.54 | 81.9 | 69.88 |
| D | 0.55 | 81.9 | 70.15 |
| E | 0.57 | 81.7 | 69.24 |
| A | 0.44 | 82.7 | 70.29 |
| F | 0.39 | 77.3 | 66.36 |
Claims (8)
1, a kind of hydrocarbons reforming catalyst, comprise carrier and be the following active ingredient of content of calculating benchmark with the carrier: VIII family metal 0.01～2.0 quality %, VIIB family metal 0.01～5.0 quality %, halogen 0.1～10.0 quality %, described carrier is made up of the aluminum oxide of 80～99 quality % and the amorphous aluminum silicide of 1～20 quality %.
2, according to the described catalyzer of claim 1, it is characterized in that VIII family metal content is 0.05～1.0 quality % in the described catalyzer, VIIB family metal content is 0.05～2.0 quality %, and content of halogen is 0.1～3.0 quality %, and the content of amorphous aluminum silicide is 5～15 quality % in the carrier.
3, according to the described catalyzer of claim 1, it is characterized in that described VIII family metal is a platinum, VIIB family metal is a rhenium, halogen is a chlorine.
4,, it is characterized in that the silicon oxide of described amorphous aluminum silicide and the mol ratio of aluminum oxide are 0.8～1.6 according to the described catalyzer of claim 1.
5, the described Preparation of catalysts method of a kind of claim 1, comprise amorphous aluminum silicide and aluminium hydrate powder are mixed aftershaping, obtain carrier after drying, the roasting, adopt step impregnation then or be total to the method for flooding and in described carrier, introduce VIII family metal and VIIB family metal.
6, in accordance with the method for claim 5, the compound that it is characterized in that flooding used VIII family metal is the water-soluble platinic compound that contains, and the compound of VIIB family metal is for containing rhenium compound.
7, in accordance with the method for claim 6, it is characterized in that the water-soluble platinic compound that contains is selected from Platinic chloride or ammonium chloroplatinate, contains rhenium compound and is selected from perrhenic acid or ammonium perrhenate.
8, the described catalyzer of claim 1 is applicable to that boiling range is the catforming process of the gasoline component of the described boiling range that produces of 40～230 ℃ virgin naphtha or its blending secondary processing process.
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|---|---|---|---|
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|---|---|---|---|
| CNB2004100963138A CN100377780C (en) | 2004-11-30 | 2004-11-30 | Reforming catalyst for hydrocarbon and preparing method |
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|---|---|
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| CN100377780C CN100377780C (en) | 2008-04-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055960C (en) * | 1997-11-24 | 2000-08-30 | 中国石油化工总公司 | Hydrocracking catalyst for moderate oil and preparation thereof |
| CN1098916C (en) * | 2000-01-04 | 2003-01-15 | 中国石油化工集团公司 | Medium oil type hydrocracking catalyst and its preparing process |
| CN1175089C (en) * | 2001-04-28 | 2004-11-10 | 中国石油化工股份有限公司 | Reforming catalyst containing molecular sieve |
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