CN102527367B - Catalyst for selective hydrogenation of cracked gasoline and preparation and application thereof - Google Patents
Catalyst for selective hydrogenation of cracked gasoline and preparation and application thereof Download PDFInfo
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- CN102527367B CN102527367B CN201010622227.1A CN201010622227A CN102527367B CN 102527367 B CN102527367 B CN 102527367B CN 201010622227 A CN201010622227 A CN 201010622227A CN 102527367 B CN102527367 B CN 102527367B
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Abstract
The invention relates to a catalyst for selective hydrogenation of cracked gasoline. The catalyst comprises a magnesium oxide-titanium oxide-aluminum oxide composite oxide serving as a carrier, a metal palladium active component loaded on the composite oxide carrier and an auxiliary metal of the IIA group and/or IIIB group metal, wherein the content of metal palladium is 0.25-0.35% by weight, the content of auxiliary metal is 0.2-3% by weight, and in the carrier, the content of magnesium oxide based on aluminum oxide is 0.1-3% by weight, and the content of titanium oxide is 5-20% by weight. The catalyst can be applied to the selective hydrogenation of cracked gasoline, and has high low-temperature activity, high selectivity, strong resistance against impurities of As, S, O and N, large gel capacity and stable activity in long-term operation. Moreover, the invention also relates to preparation of the catalyst and application in the selective hydrogenation of cracked gasoline. Finally, the invention also relates to a method for preparing the composite oxide carrier by a parallel-flow coprecipitation method.
Description
Technical field
The present invention relates to a kind of petroleum hydrocarbon and select to add catalyst for hydrogen, particularly drippolene C
5-C
9cut, especially C
8-C
9heavy distillat selects to add catalyst for hydrogen.The invention still further relates to preparation method and the application thereof of this catalyst.
Background technology
Drippolene C
5-C
9cut is the accessory substance of ethylene industry, and according to the difference of cracking stock and cracking severity, more than its output accounts for 50 % by weight of ethylene production capacity, wherein arene content accounts for 40-80 % by weight, is therefore the main source of aromatic hydrocarbons.In industrial production, cut C
8and C
9cut, through one-stage hydrogenation, removes height unsaturated hydrocarbons, as chain conjugated diene, styrene, alkynes and cyclic conjugated diene class, then through Secondary hydrodesulfurization, removes after the organic compounds such as monoene and sulphur, nitrogen, oxygen C
8cut is for the production of dimethylbenzene, and C
9cut is for the production of aromatic solvent naphtha.C
8cut also can be removed diolefin only through a hydrogenation, retains most of monoene, obtains stable motor petrol adulterant or the higher motor petrol of octane number.
Current industrial drippolene C
5-C
9fraction selective hydrogenation is mainly Ni/Al with catalyst
2o
3or Pd/Al
2o
3, also have Pd-Cr/Al
2o
3bimetallic catalyst.Due to drippolene C
8and C
9in heavy distillat, the impurity such as As, S, O, N and gum level are higher, make the very fast inactivation of catalyst, thereby catalyst have to frequent activation and regeneration.The Pd/Al of present industrial use
2o
3the shortest regeneration period of catalyst is 7 days.Therefore, wish that hydrogenation catalyst has higher low temperature active, higher anti-impurity poisoning capability and suitable appearance glue ability, to increase the catalyst regeneration cycle, thus extending catalyst service life, this is very important in industrial production.
The open CN1443829A of Chinese patent application discloses one section of selective hydrogenation catalyst of a kind of drippolene and method for making thereof, the 0.05-0.4% that wherein load capacity of active component Pd is catalyst weight, and active component palladium is eggshell type at carrier surface and distributes, and shell thickness is 0.03-0.09mm; Its carrier is alumina support, and crystalline phase is δ phase, and the pore volume of carrier is 0.6-0.9ml/g, and specific area is 140-170m
2/ g.This catalyst is compared with the granular catalyst of industrial current employing, can effectively reduce the pressure drop of reaction bed, be conducive to reaction and remove heat, make bed temperature more even, be conducive to improve the selective of object product, adapt to high-speed running, and there is good stability, but its activity and selectivity still leaves some room for improvement.
US Patent No. 6,576,586 disclose a kind of pyrolysis gasoline selective hydrogenation catalyst that can move under high-speed, the 0.05-0.4% that wherein load capacity of active component Pd is catalyst weight, take alkali metal or/and alkaline-earth metal is auxiliary agent, its load capacity is the 0.05-2.0% of catalyst weight, and carrier is to have δ phase to mix mutually the Al of phase with α
2o
3, α phase Al wherein
2o
3account for 0.5-5wt%, the pore volume of carrier is 0.5-0.9ml/g, and aperture is distributed in 4-20nm mostly, and specific area is 70-140m
2/ g.Yet, the low temperature active of this catalyst and selectively all having much room for improvement.
The open CN1361231A of Chinese patent application discloses a kind of catalyst for selective hydrogenation of diolefin as, the aluminium titanium composite oxide carrier of its carrier for adopting chemical coprecipitation to prepare, wherein the weight percent content of aluminium oxide is 1-99%, carrier aperture is distributed in 50nm and 1000nm place occurs bimodal, load P d active component and optional IB and/or IAHuo IIA family metal, there is the advantages such as active high, selective height, anti-sulphur and arsenic ability are strong, but its low temperature active still haves much room for improvement.
In order to overcome the above-mentioned problems in the prior art, the present inventor discloses a kind of catalyst of selecting hydrogenation for heavy fraction of pyrolysis gasoline in the open CN1635054A of Chinese patent application, it comprises the aluminium oxide as carrier, and be carried on activity component metal Pd and Mo or Pd and the W on this carrier, be covered in alkaline-earth metal or its oxide on described carrier surface, wherein the content of alkaline-earth metal is 1-3 % by weight based on described total catalyst weight, the content of Pd is 0.24-0.35 % by weight based on described total catalyst weight, the weight ratio of Pd and Mo or Pd and W is 1: 0.5-2.5, the crushing strength of this catalyst is greater than 18N/mm.This catalyst can be used for drippolene C
5-C
9cut, particularly C
8-C
9the selection hydrogenation of heavy distillat, its low temperature active is high, and anti-As, S, O, N impurity ability are strong, and charging capacity is large and activity stabilized.Yet its selectivity still haves much room for improvement.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly to selective hydrogenation of cracked gasoline with catalyst, found that by improving carrier preparation method and adding that Pd that auxiliary agent makes is catalyst based has better low temperature active, selective and stability.The present invention is accomplished based on above discovery just.
Therefore, the object of this invention is to provide a kind of new catalyst for selective hydrogenation of cracked gasoline, this catalyst has advantages of high, the anti-impurity ability of low temperature active and holds that glue ability is high, selective good and good stability.
Another object of the present invention is to provide a kind of method of preparing above-mentioned catalyst.
A further object of the present invention is to provide a kind of method of drippolene being selected to hydrogenation.
Another object of the present invention is to provide a kind of method of preparing magnesia-titania-alumina composite oxide, and composite oxides prepared by the method are particularly suitable for the carrier as catalyst of the present invention.
Therefore, one aspect of the present invention provides a kind of catalyst for selective hydrogenation of cracked gasoline, it comprises the magnesia-titania-alumina composite oxide as carrier, and be carried on activity component metal palladium on described composite oxide carrier and one or more are selected from the promoter metal of IIAZu He IIIB family metal, wherein the content of Metal Palladium is 0.25-0.35 % by weight based on described total catalyst weight, the content of described promoter metal is 0.2-3 % by weight based on described total catalyst weight, and in carrier, magnesian content is 0.1-3 % by weight based on alumina weight, and the content of titanium oxide is 5-20 % by weight based on alumina weight.
The present invention provides a kind of method of preparing above-mentioned catalyst on the other hand, comprises the steps:
(a) magnesia-titania-alumina composite oxide carrier is used at least and flooded with the promoter metal compound solution of this composite oxide carrier pore volume equivalent, this promoter metal is to be selected from one or more in IIAZu He IIIB family metal, by carrier drying and roasting through dipping, make catalyst semi-finished product, based on the half-finished gross weight of this catalyst, the content of promoter metal is 0.2-3 % by weight, and the calcium that preferably these catalyst semi-finished product contain 1-3 % by weight and the yttrium of 0-1 % by weight are as promoter metal;
(b) solution impregnation with palladium source compound by the catalyst semi-finished product of preparation in step (a), then uses hydrazine hydrate (N
2h
4.H
2o) reduction, washing, dry and roasting, makes palladium supported catalyst afterwards, and the palladium metal content of this catalyst is 0.25-0.35 % by weight, and promoter metal content is 0.2-3 % by weight; And
(c) by step (b) gained palladium supported catalyst, in temperature, be optionally, that 100-150 ℃, Hydrogen Vapor Pressure are that 2.0-3.0MPa and hydrogen flowing quantity are to reduce under the condition of 2-15ml/min.g catalyst.
It is a kind of to drippolene that further aspect of the present invention provides, preferably drippolene C
5-C
9cut, especially C
8and C
9the method of hydrogenation is selected in heavy distillat, comprising:
(1) in temperature, be optionally, that 100-150 ℃, Hydrogen Vapor Pressure are that 2.0-3.0MPa and hydrogen flowing quantity are under the condition of 2-15ml/min.g catalyst, to reduce catalyst of the present invention; And
(2) in temperature, be that 50-60 ℃, pressure are that 2.6-3.0MPa, hydrogen to oil volume ratio are 50: 1-80: 1 and liquid hourly space velocity (LHSV) be 8-12h
-1condition under hydrocrack gasoline.
Another aspect of the present invention also provides a kind of the present invention of preparation the method for magnesia-titania-alumina composite oxide carrier used, comprising:
(i) preparation comprise magnesium compound, titanium compound and aluminium compound mixed solution, wherein based on aluminium compound with Al
2o
3the weight of meter, it is 0.1-3 % by weight that described magnesium compound be take the content of MgO, and titanium compound is with TiO
2the content of meter is 5-20 % by weight;
(ii) adopt co-precipitation method, at the temperature of 10-60 ℃, under agitation in adding step (i), in prepared mixed solution, add (NH
4)
2cO
3the aqueous solution or ammonia spirit, with ammoniacal liquor or (NH
4)
2cO
3the aqueous solution regulates reactant mixture to pH=7-9, forms precipitation; And
(iii) gained precipitation in separating step (ii), by separated precipitation, dry and roasting, obtains magnesia-titania-alumina composite oxide carrier.
It is more clear that these and other purposes, features and advantages of the present invention will become after reading this description.
In catalyst for selective hydrogenation of cracked gasoline of the present invention, comprise active metal component palladium, palladium loads on magnesia-titania-alumina composite oxide.Gross weight based on catalyst, the content of Metal Palladium is generally 0.25-0.35 % by weight, preferably 0.27-0.33 % by weight.
In addition, catalyst for selective hydrogenation of cracked gasoline of the present invention also comprises one or more promoter metal that is selected from IIAZu He IIIB family metal, and this promoter metal loads on magnesia-titania-alumina composite oxide.As IIA family metal, can be one or more in magnesium, calcium, strontium and barium, be particularly preferably calcium.As IIIB family metal, can be one or more in scandium, yttrium, lanthanide series metal (as lanthanum and cerium), be particularly preferably yttrium.In a preferred embodiment of catalyst of the present invention, as promoter metal, preferably both used IIA family metal, use again IIIB family metal.Gross weight based on catalyst, the total content of described promoter metal is generally 0.2-3 % by weight, preferably 2-3 % by weight.
In the particularly preferred embodiment of catalyst of the present invention, as described promoter metal, the yttrium of the calcium that catalyst of the present invention comprises 1-3 % by weight and 0-1 % by weight, the gross weight based on catalyst.
Advantageously, the crushing strength of catalyst for selective hydrogenation of cracked gasoline of the present invention is greater than 18N/mm.
Catalyst of the present invention is loaded catalyst, active metal component palladium wherein and as the IIA family of promoter metal and/or IIIB family Metal Supported on magnesia-titania-alumina composite oxide carrier.In being suitable for the magnesia-titania-alumina composite oxide carrier of catalyst of the present invention, weight based on aluminium oxide, magnesian content is generally 0.1-3 % by weight, preferably 0.5-3 % by weight, the content of titanium oxide is generally 5-20 % by weight, preferably 10-20 % by weight.Advantageously, the weight based on aluminium oxide, magnesian content is 0.5-3 % by weight, the content of titanium oxide is 10-20 % by weight.
In a preferred embodiment of catalyst of the present invention, the specific area of magnesia-titania-alumina composite oxide carrier is 80-180m
2/ g, most probable aperture is 9-19nm, and pore volume is 0.4-1.3ml/g.
In the present invention, crushing strength refers to side crush intensity, by intensity of pressure instrument, measures; Specific area, most probable aperture and pore volume adopt nitrogen physisorption method to measure.
For magnesia-titania-alumina composite oxide carrier of the present invention, be particularly suitable for preparing by carrier preparation method of the present invention.
In order to prepare magnesia-titania-alumina composite oxide carrier, first, in step (i), prepare the mixed solution that comprises magnesium compound, titanium compound and aluminium compound.The content of the magnesium compound in this mixed solution, titanium compound and aluminium compound should make: based on aluminium compound with Al
2o
3the weight of meter, it is 0.1-3 % by weight that magnesium compound be take the content of MgO, preferred 0.5-3 % by weight, and titanium compound is with TiO
2the content of meter is 5-20 % by weight, preferably 10-20 % by weight.Preferably, based on aluminium compound with Al
2o
3the weight of meter, it is 0.5-3 % by weight that magnesium compound be take the content of MgO, and titanium compound is with TiO
2the content of meter is 10-20 % by weight.In order to form described mixed solution, as solvent, can make water, methyl alcohol, ethanol or its mixture as solvent, preferably make water as solvent.As described titanium compound, can use one or more titanium salts in acetate, hydrochloride and the nitrate that is selected from titanium or be selected from one or more titanate esters in tetraethyl titanate, metatitanic acid four n-propyls and tetra-n-butyl titanate, preferably titanium tetrachloride.As described magnesium compound, can use and be selected from magnesium nitrate (as Mg (NO
3)
26H
2o), one or more in magnesium chloride, magnesium sulfate and their hydrate.As described aluminium compound, can use and be selected from aluminum nitrate (as Al (NO
3)
39H
2o), one or more in aluminium chloride, aluminum sulfate and their hydrate.Described mixed solution be take concentration conventionally as 0.1-5mol/L, preferably 1-2mol/L use.
In a carrier preparation method's of the present invention preferred embodiment, the preparation of mixed solution described in step (i) comprises:
(1) titanium compound is dissolved in deionized water or ethanol, is mixed with the compound titanium solution S of 0.1-1mol/L
ti,
(2) aluminium compound is dissolved in deionized water or ethanol, is mixed with the aluminum compound solution S of 1-5mol/L
al,
(3) magnesium compound is dissolved in deionized water or ethanol, is mixed with the magnesium compound solution S of 0.01-1mol/L
mg, and
(4) by solution S
ti, S
aland S
mgaccording to required ratio, mix, obtain mixed solution described in step (i).
After making the mixed solution that comprises magnesium compound, titanium compound and aluminium compound, in step (ii), adopt co-precipitation method, at the temperature of 10-60 ℃, under agitation in adding step (i), in prepared mixed solution, add (NH
4)
2cO
3the aqueous solution or ammonia spirit, with ammoniacal liquor or (NH
4)
2cO
3the aqueous solution regulates reactant mixture to pH=7-9, forms precipitation.
In the present invention, so-called co-precipitation method refers to, prepared mixed solution and (NH in step (i)
4)
2cO
3the aqueous solution or ammonia spirit adopt and the mode that flows is fed in raw material, and are divided into two stock materials streams and feed simultaneously, the rear precipitation that generates of two stock materials stream contacts.The temperature of this co-precipitation reaction is generally 10-60 ℃, and this for example by carrying out in water bath with thermostatic control.This co-precipitation needs to stir conventionally, for example mechanical agitation, magnetic agitation or ultrasonic agitation, preferably magnetic agitation.(NH
4)
2cO
3the aqueous solution conventionally be take the aqueous solution that concentration is 0.1-2mol/L and is used, and ammonia spirit conventionally be take the aqueous solution that concentration is 0.1-1mol/L and used.Preferably, the interpolation speed of mixed solution is (NH
4)
2cO
3the aqueous solution or ammonia spirit add 0.1-2 times of speed.For example, the interpolation speed of mixed solution be 60-80 drip/minute, (NH
4)
2cO
3the rate of addition of the aqueous solution or ammonia spirit be 30-40 drip/minute.When reactant mixture pH value is 7-9, can advantageously generate precipitation, this precipitates roasting subsequently can produce magnesia-titania-alumina composite oxide.Described pH value both can be added (NH at the same time
4)
2cO
3in the aqueous solution or ammonia spirit and step (i), producing during prepared mixed solution, can be also with ammoniacal liquor or (NH after mixed solution prepared in adding step (i)
4)
2cO
3the aqueous solution regulates and obtains.
After obtaining precipitation, in step (iii), gained precipitation in separating step (ii), by separated precipitation, dry and roasting, obtains magnesia-titania-alumina composite oxide carrier.Described being dried carried out conventionally at 50-120 ℃, is generally 1-24 hour drying time.Subsequently, by the precipitation roasting of drying, this is advantageously by realizing in the roasting temperature of 450-600 ℃, and roasting time is generally 2-6 hour, thereby obtains magnesia-titania-alumina composite oxide carrier.Advantageously, gained in step (ii) is deposited in to ageing under room temperature, suction filtration and washing in its mother liquor, and then dry and roasting.The specific area of the magnesia-titania-alumina composite oxide carrier obtaining after roasting is 80-180m
2/ g, most probable aperture is 9-19nm, and pore volume is 0.4-1.3ml/g.
In the preparation method of catalyst of the present invention, first carry out step as above (a), in this step, used magnesia-titania-alumina composite oxide carrier.As described in for catalyst of the present invention, in described composite oxide carrier, the weight based on aluminium oxide, magnesian content is generally 0.1-3 % by weight, preferred 0.5-3 % by weight, the content of titanium oxide is generally 5-20 % by weight, preferably 10-20 % by weight.Advantageously, the weight based on aluminium oxide, magnesian content is 0.5-3 % by weight, the content of titanium oxide is 10-20 % by weight.In addition also advantageously, the specific area of composite oxide carrier used is 80-180m
2/ g, most probable aperture is 9-19nm, and pore volume is 0.4-1.3ml/g.Particularly preferably being, is to prepare by the method for preparing magnesia-titania-alumina composite oxide carrier of the present invention for the preparation of the magnesia-titania-alumina composite oxide carrier of catalyst of the present invention.
The step of method for preparing catalyst of the present invention (a) is, magnesia-titania-alumina composite oxide carrier is used at least and flooded with the promoter metal compound solution of this composite oxide carrier pore volume equivalent, this promoter metal is to be selected from one or more in IIAZu He IIIB family metal, by carrier drying and roasting through dipping, make catalyst semi-finished product, based on the half-finished gross weight of this catalyst, the content of promoter metal is 0.2-3 % by weight, and the calcium that preferably these catalyst semi-finished product contain 1-3 % by weight and the yttrium of 0-1 % by weight are as promoter metal.
In the promoter metal compound solution using in above-mentioned steps (a), the solvent that is used to form this solution use can be for example water, nitric acid, hydrochloric acid, ammoniacal liquor or its mixture, can also be with an organic solvent, as ethanol, methyl alcohol, benzene, oxalic acid, acetic acid or its mixture etc., preferably make water as solvent.
As the promoter metal compound using in above-mentioned steps (a), can be that any can dissolving forms the IIA family of solution and/or the compound of IIIB family metal, these compounds decomposed in the roasting stage subsequently, correspondingly obtained the oxide of IIA family and/or IIIB family metal.For the promoter metal of mentioning, be preferably selected from one or more in magnesium, calcium, strontium, barium, scandium, yttrium and lanthanide series metal (as lanthanum and cerium) herein.As this promoter metal compound, can mention any organic and inorganic salts of IIA family and/or IIIB family metal.And then, as IIA family metallic compound, for example, can use nitrate, sulfate, chloride, acylate and/or the acetylacetonate of magnesium, calcium, strontium, barium, preferably magnesium nitrate, calcium nitrate, strontium nitrate and/or barium nitrate; As IIIB family metallic compound, for example, can use nitrate, sulfate, chloride, acylate and/or the acetylacetonate of scandium, yttrium, lanthanide series metal, preferably scandium nitrate, yttrium nitrate, lanthanum nitrate and/or cerous nitrate.It is 0.05-5mol/L that promoter metal compound solution preferably be take promoter metal compound total concentration, and preferably the solution (preferred aqueous solutions) of 0.1-4mol/L is used.
In order to carry out the dipping in step (a), conventionally magnesia-titania-alumina composite oxide carrier is immersed to a period of time, for example 5-20 minute in promoter metal compound solution.This process is advantageously under agitation carried out, and is beneficial to the abundant dipping of carrier.After dipping, unnecessary maceration extract is removed in leaching, and by the carrier drying through dipping of gained, this keeps a period of time to realize conventionally at the temperature of 100-150 ℃, for example, conventionally keep realizing for 8-12 hour.Then, by the composite oxide carrier roasting of drying, promoter metal compound is transformed into the oxide of promoter metal, this keeps a period of time to realize conventionally at the temperature of 500-600, for example, conventionally keep realizing for 3-6 hour.After roasting, make catalyst semi-finished product.After making as mentioned above catalyst semi-finished product, carry out step as above (b), that is, the solution impregnation by the catalyst semi-finished product of preparation in step (a) with palladium source compound, then uses hydrazine hydrate (N
2h
4.H
2o) reduction, washing, dry and roasting, makes palladium supported catalyst afterwards, and the palladium metal content of this catalyst is 0.25-0.35 % by weight, and promoter metal content is 0.2-3 % by weight.In the solution of the palladium source compound using in step (b), the solvent that is used to form this solution use can be water, methyl alcohol, ethanol or its mixture, preferably makes water as solvent.Palladium source compound as using in above-mentioned steps (b), can be used any palladium compound that is suitable for preparing palladium catalyst, as palladium bichloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, tetranitro palladium acid sodium, H
2pdCl
4, the acylate (as oxalic acid palladium) of palladium or its mixture etc.These palladium source compounds preferably be take concentration as 0.15-0.75g/ml, the more preferably solution of 0.2-0.7g/ml (preferred aqueous solutions) use.The consumption of palladium source compound solution is answered the catalyst semi-finished product of preparation in submergence step (a), and preferably its consumption is the solution that every gram of catalyst semi-finished product are used 0.5-3ml palladium source compound.In step (a), the catalyst semi-finished product of preparation are used the solution impregnation 0.5-2 hour of palladium source compound conventionally.
In above-mentioned steps (b), after dipping, use hydrazine hydrate reduction, so that palladium source compound is reduced.For this reason, hydrazine hydrate is preferably used as ethanolic solution with the aqueous solution of 30-40 % by weight or alcoholic solution, and preferably the aqueous solution with 30-40 % by weight is used.The consumption of hydrazine hydrate solution is answered the catalyst semi-finished product of preparation in submergence step (a), and preferably its consumption is that every gram of catalyst semi-finished product are used 1-3ml hydrazine hydrate solution.With the reduction of hydrazine hydrate, conventionally at 10-60 ℃ of temperature, carry out, the time is generally 0.1-2 hour.After reduction, separation, for example, by isolated by filtration, and water, preferably deionized water, washs.For example, in the situation that using palladium bichloride as palladium source compound, by deionized water, fully wash, until without chlorion, this checks to carry out by liquor argenti nitratis ophthalmicus.After washing, the washed product of gained is dry at 100-150 ℃, and this carries out 4-8 hour conventionally.Then, by the roasting at 450-600 ℃ of the product of drying, this carries out 3-8 hour conventionally, makes palladium supported catalyst.
In step (b) afterwards, the palladium supported catalyst obtaining in step (b) is activated with hydrogen reducing.As selection, the palladium supported catalyst obtaining in step (b) also can be when for drippolene hydrogenation reactivation.That is to say, in preparing the method for catalyst of the present invention, step (c) is not the step that must carry out.
If carry out step (c), the activation of the palladium supported catalyst in step (c) is that 100-150 ℃, Hydrogen Vapor Pressure are that 2.0-3.0MPa and hydrogen flowing quantity are also originally to carry out under the condition of 2-15ml/min.g catalyst by it in temperature conventionally, preferably reduces 6-8h.
Catalyst of the present invention can be used for the selection hydrogenation of drippolene, is particularly suitable for drippolene C
5-C
9cut, especially C
8and C
9the selection hydrogenation of heavy distillat.For this, select hydrogenation, first optionally catalyst of the present invention is activated with hydrogen reducing.If the words of carrying out, this reduction activation is by being that 100-150 ℃, Hydrogen Vapor Pressure are that 2.0-3.0MPa and hydrogen flowing quantity are to reduce a period of time under the condition of 2-15ml/min.g catalyst to carry out by catalyst of the present invention in temperature, preferably reduction 6-8 hour, carries out step (i).Should be understood that, if in catalyst preparation process, that catalyst reduction is active, do not carry out step (c),, in method of drippolene being carried out to selective hydrogenation of the present invention, must carry out the reduction activation in step (i).Then, in temperature, be that 50-60 ℃, pressure are that 2.6-3.0MPa, hydrogen to oil volume ratio are 50: 1-80: 1 and liquid hourly space velocity (LHSV) be 8-12h
-1condition under hydrocrack gasoline.
In selection method of hydrotreating of the present invention, described drippolene is that diene value is that 20-40g iodine/100g oil and bromine valency are the drippolene raw material of 40-70g bromine/100g oil.
Catalyst of the present invention is for drippolene C
5-C
9cut, especially C
8and C
9the selection hydrogenation of heavy distillat has following outstanding advantages and effect:
1. the low temperature hydrogenation activity of catalyst of the present invention is high, selectively high.
2. catalyst appearance colloidality of the present invention can be good, and hydrogenation activity is stable, and life cycle is long.
Embodiment
Below by embodiment, the present invention has been carried out to further elaboration, but these embodiment are in no case construed as limiting to scope of the present invention.
Embodiment 1
Step 1
(1) use TiCl
4tiCl with deionized water preparation 0.25mol/L
4the aqueous solution (A);
(2) use Al (NO
3)
39H
2o crystal and the aluminum nitrate aqueous solution (B) that removes dried up preparation 1.55mol/L;
(3) use Mg (NO
3)
26H
2o and the magnesium nitrate aqueous solution (C) that removes dried up preparation 0.025mol/L;
(4) according to based on aluminum nitrate with Al
2o
3the weight TiCl of meter
4with TiO
2the content of meter is that 20 % by weight and magnesium nitrate be take the amount that the content of MgO is 1 % by weight, and solution A, B and C are mixed, and obtains the mixed solution (D) containing Mg, Ti and Al;
(5) adopt co-precipitation method, in the water bath with thermostatic control of 40 ℃, under magnetic agitation, drip (the NH of 0.5mol/L simultaneously
4)
2cO
3the aqueous solution and the mixed solution (D) containing Mg, Ti and Al of preparing, wherein the rate of addition of mixed solution (D) is 60 droplets/minute, (NH
4)
2cO
3the rate of addition of the aqueous solution is 30 droplets/minute; Ammoniacal liquor with 0.5mol/L after being added dropwise to complete regulates the acid-base value of reactant mixture to pH=8, forms white precipitate;
(6) by the white precipitate of gained in its mother liquor under room temperature ageing 12h, suction filtration, with deionized water washing to without Cl
-, then put into baking oven at 100 ℃ dry 12 hours, 500 ℃ of roasting temperatures 4 hours, obtain magnesia-titanium dioxide-alumina composite oxide carrier (hereinafter referred is " MgTiAl complex carrier ").In this carrier, the weight based on aluminium oxide, the content of MgO is 1 % by weight, TiO
2content be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Step 2
Get the MgAlTi complex carrier of preparation in 97g step 1, add wherein (the 0.14g/ml containing calcium nitrate 3.5mol/L, in calcium) and yttrium nitrate 0.168mol/L (0.015g/ml, using yttrium) mixed aqueous solution 90ml as maceration extract, stir 15 minutes, unnecessary maceration extract is removed in leaching, then at 120 ℃ of dry 10h, at 550 ℃ of roasting 4h, make the catalyst semi-finished product containing the calcium of 2.2 % by weight and the yttrium of 0.29 % by weight, based on the half-finished gross weight of this catalyst.
Step 3
The catalyst semi-finished product of preparation in 100g step 2 are immersed in the palladium chloride aqueous solution that 85ml concentration is 0.509g/ml, after 1 hour, take out, drain, at 30 ℃, with the hydrazine hydrate aqueous solution that 120ml concentration is 40 % by weight, reduce 1 hour, by deionized water, wash extremely without chlorion, at 120 ℃ dry 6 hours, then roasting 4 hours at 480 ℃, made palladium-based catalyst A.
The palladium content of palladium-based catalyst A is 0.3 % by weight, and calcium content is 2.2 % by weight, and yttrium content is 0.29 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight, TiO
2the weight of content based on aluminium oxide be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Embodiment 2
The step 1-3 that repeats embodiment 1, different: in the sub-step (4) of step 1, according to based on aluminum nitrate with Al
2o
3the weight TiCl of meter
4with TiO
2the content of meter is that 5 % by weight and magnesium nitrate be take the amount that the content of MgO is 3 % by weight, and solution A, B and C are mixed, and obtains the mixed solution (D) containing Mg, Ti and Al.
As a result, in the magnesia-titanium dioxide-alumina composite oxide carrier obtaining in step 1, the weight based on aluminium oxide, the content of MgO is 3 % by weight, TiO
2content be 5 % by weight; And the specific area of this carrier is 132m
2/ g, most probable aperture is 18.5nm, pore volume is 0.5ml/g.
As a result, through step 3, obtain palladium-based catalyst B.The palladium content of palladium-based catalyst B is 0.3 % by weight, and calcium content is 2.2 % by weight, and yttrium content is 0.29 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 3 % by weight, TiO
2the weight of content based on aluminium oxide be 5 % by weight; And the specific area of this carrier is 132m
2/ g, most probable aperture is 18.5nm, pore volume is 0.5ml/g.
Embodiment 3
The step 1-3 that repeats embodiment 1 is different: the calcium nitrate aqueous solution that the maceration extract of the dipping complex carrier using in step 2 is changed to the 3.5mol/L (0.14g/ml, in calcium) that makes 90ml.
As a result, the catalyst semi-finished product that obtain in step 2 contain the calcium of 2.2 % by weight, and obtain palladium-based catalyst C through step 3.The palladium content of palladium-based catalyst C is 0.3 % by weight, and calcium content is 2.2 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight, TiO
2the weight of content based on aluminium oxide be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Embodiment 4
The step 1-3 that repeats embodiment 1 is different: the yttrium nitrate aqueous solution that the maceration extract of the dipping complex carrier using in step 2 is changed to the 0.168mol/L (0.015g/ml, in yttrium) that makes 90ml.
As a result, the catalyst semi-finished product that obtain in step 2 contain the yttrium of 0.29 % by weight, and obtain palladium-based catalyst D through step 3.The palladium content of palladium-based catalyst D is 0.3 % by weight, and yttrium content is 0.29 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight, TiO
2the weight of content based on aluminium oxide be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Embodiment 5
The step 1-3 that repeats embodiment 1 is different: the maceration extract of the dipping complex carrier using in step 2 is changed and makes 90ml deionized water.
As a result, the catalyst semi-finished product that obtain in step 2 are calcic and yttrium not, and obtains catalyst E through step 3.The palladium content of palladium-based catalyst E is that 0.3 % by weight, crushing strength are 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight, TiO
2the weight of content based on aluminium oxide be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Embodiment 6
Repeat the step 1-3 of embodiment 1, different: the maceration extract of the dipping complex carrier using in step 2 is changed and done containing calcium nitrate 3.5mol/L (0.14g/ml, in calcium) and the mixed aqueous solution 90ml of cerous nitrate 0.168mol/L (0.024g/ml, in cerium).
As a result, the catalyst semi-finished product that obtain in step 2 contain the calcium of 2.2 % by weight and the cerium of 0.2 % by weight, and obtain palladium-based catalyst F through step 3.The palladium content of palladium-based catalyst F is 0.3 % by weight, and calcium content is 2.2 % by weight, and cerium content is 0.2 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight, TiO
2the weight of content based on aluminium oxide be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Embodiment 7
Repeat the step 1-3 of embodiment 1, different: the maceration extract of the dipping complex carrier using in step 2 is changed and done containing strontium nitrate 3.5mol/L (0.31g/ml, in strontium) and the mixed aqueous solution 90ml of yttrium nitrate 0.168mol/L (0.015g/ml, in yttrium).
As a result, the catalyst semi-finished product that obtain in step 2 contain the strontium of 2 % by weight and the yttrium of 0.29 % by weight, and obtain palladium-based catalyst G through step 3.The palladium content of palladium-based catalyst G is 0.3 % by weight, and content of strontium is 2 % by weight, and yttrium content is 0.29 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight, TiO
2the weight of content based on aluminium oxide be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable aperture is 18nm, pore volume is 0.52ml/g.
Embodiment 8
The step 1-3 that repeats embodiment 1, different: omit the sub-step (1) of step 1, and in the sub-step (4) of step 1, according to based on aluminum nitrate with Al
2o
3the weight nitric acid magnesium of meter be take the amount that the content of MgO is 1 % by weight, and solution B and C are mixed, and obtains the mixed solution (D) containing Mg and Al.
As a result, in the magnesia-alumina composite oxide carrier obtaining in step 1, the weight based on aluminium oxide, the content of MgO is 1 % by weight; The specific area of this carrier is 135m
2/ g, most probable aperture is 19nm, pore volume is 0.59ml/g.
As a result, the catalyst semi-finished product that obtain through step 2 are containing the calcium of 2.2 % by weight and the yttrium of 0.29 % by weight.
As a result, through step 3, obtain palladium-based catalyst H.The palladium content of palladium-based catalyst H is 0.3 % by weight, and calcium content is 2.2 % by weight, and yttrium content is 0.29 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the weight of the content of MgO based on aluminium oxide is 1 % by weight; And the specific area of this carrier is 135m
2/ g, most probable aperture is 19nm, pore volume is 0.59ml/g.
The content of catalyst A-H IIAZu He IIIB family metal promoter is separately in Table 1.
Table 1
Note: the catalyst with * is comparative catalyst.
Embodiment 9
The catalyst of the present embodiment explanation embodiment 1-8 gained is at drippolene C
8application in fraction selective hydrogenation.
Evaluating catalyst experiment is carried out on 100ml small fixed hydrogenation evaluating apparatus, and the reactor of this evaluating apparatus is reaction tube, reaction tube length 1.2m, and internal diameter 26mm, loaded catalyst is 100ml.
Getting each 100ml of catalyst A-H that embodiment 1-8 makes and be loaded into respectively in the reaction tube of hydrogenation evaluating apparatus, is 2.8MPa at Hydrogen Vapor Pressure, and temperature is that 110 ℃ and hydrogen flowing quantity are to reduce 8 hours under the condition of 4ml/min.g catalyst.Then cooling, is 2.8Mpa at Hydrogen Vapor Pressure afterwards, and reaction temperature is 50 ℃, and hydrogen to oil volume ratio is 80: 1, and total liquid hourly space velocity (LHSV) is 12h
-1condition under to pass into diene value be that 20.27g iodine/100g oil, bromine valency are that 40.36g bromine/100g oil, gum level are that 232mg/100ml oil, nitrogen content are that 3.4mg/100ml oil, oxide content are that 2.19g/100ml oil, sulfur content are the drippolene C that 110ppm and arsenic content are 180ppb
8cut, hydrogenation the results are shown in Table 2.
Table 2
Embodiment 10
Get the catalyst A 100ml that embodiment 1 makes, be packed in 100ml small fixed hydrogenation evaluating apparatus, the reactor of this device is reaction tube, reaction tube length 1.2m, and internal diameter is 26mm.The process conditions such as reaction temperature, pressure are by microcomputer automatic control.After Catalyst packing completes, at Hydrogen Vapor Pressure, be 2.8MPa, temperature is that 110 ℃ and hydrogen flowing quantity are to reduce 8 hours under the condition of 4ml/min.g catalyst.Then cooling, is 2.8MPa at Hydrogen Vapor Pressure afterwards, and reaction temperature is 50 ℃, and hydrogen to oil volume ratio is 80: 1, and feeding liquid hourly space velocity is 8h
-1condition under to pass into diene value be that 20.27g iodine/100g oil, bromine valency are that 40.36g bromine/100g oil, gum level are that 232mg/100ml oil, nitrogen content are that 3.4mg/100ml oil, oxide content are that 2.19g/100ml oil, sulfur content are the drippolene C8 cut that 110ppm and arsenic content are 180ppb, fresh feed liquid hourly space velocity (LHSV) is 2.0 o'clock
-1, in 1000 hours reaction time, hydrogenation result is as following table 3.
Table 3
| Reaction time (h) | Diene in product (g iodine/100g oil) | Product bromine valency (g bromine/100g oil) |
| 100 | 0.12 | 15.8 |
| 200 | 0.16 | 18.1 |
| 400 | 0.31 | 18.4 |
| 600 | 0.31 | 18.9 |
| 800 | 0.35 | 18.8 |
| 1000 | 0.45 | 19.5 |
Known according to table 3 column data, catalyst A has good stability.
Claims (21)
1. the catalyst for selective hydrogenation of cracked gasoline, it comprises the magnesia-titania-alumina composite oxide as carrier, and be carried on activity component metal palladium on described composite oxide carrier and one or more are selected from the promoter metal of IIAZu He IIIB family metal, wherein the content of Metal Palladium is 0.25-0.35 % by weight based on described total catalyst weight, the content of described promoter metal is 0.2-3 % by weight based on described total catalyst weight, and in carrier, magnesian content is 0.1-3 % by weight based on alumina weight, and the content of titanium oxide is 5-20 % by weight based on alumina weight.
2. catalyst according to claim 1, the specific area of wherein said composite oxide carrier is 80-180m
2/ g, most probable aperture is 9-19nm, and pore volume is 0.4-1.3ml/g.
3. catalyst according to claim 1 and 2, the calcium that wherein this catalyst comprises 1-3 % by weight and the yttrium of 0-1 % by weight be as promoter metal, the gross weight based on catalyst.
4. a method of preparing the magnesia-titania-alumina composite oxide carrier described in claim 1 or 2, comprising:
(i) preparation comprise magnesium compound, titanium compound and aluminium compound mixed solution, wherein based on aluminium compound with Al
2o
3the weight of meter, it is 0.1-3 % by weight that described magnesium compound be take the content of MgO, and titanium compound is with TiO
2the content of meter is 5-20 % by weight;
(ii) adopt co-precipitation method, at the temperature of 10-60 ℃, under agitation in adding step (i), in prepared mixed solution, add (NH
4)
2cO
3the aqueous solution or ammonia spirit, with ammoniacal liquor or (NH
4)
2cO
3the aqueous solution regulates reactant mixture to pH=7-9, forms precipitation; And
(iii) gained precipitation in separating step (ii), by separated precipitation, dry and roasting, obtains magnesia-titania-alumina composite oxide carrier.
5. according to the method for claim 4, wherein the roasting in step (iii) is carried out at 450-600 ℃.
6. according to the method for claim 4, wherein 2-6 hour is carried out in the roasting in step (iii).
7. according to the method for claim 5, wherein 2-6 hour is carried out in the roasting in step (iii).
8. according to the method for any one in claim 4-7, wherein said titanium compound is one or more titanium salts of the acetate, hydrochloride and the nitrate that are selected from titanium or is selected from one or more titanate esters in tetraethyl titanate, metatitanic acid four n-propyls and tetra-n-butyl titanate, and/or magnesium compound is to be selected from one or more in magnesium nitrate, magnesium chloride and magnesium sulfate; And/or aluminium compound is to be selected from one or more in aluminum nitrate, aluminium chloride and aluminum sulfate.
9. prepare according to a method for catalyst described in claim 1 or 2, comprising:
(a) magnesia-titania-alumina composite oxide carrier is used at least and flooded with the promoter metal compound solution of this composite oxide carrier pore volume equivalent, this promoter metal is to be selected from one or more in IIAZu He IIIB family metal, by carrier drying and roasting through dipping, make catalyst semi-finished product, based on the half-finished gross weight of this catalyst, the content of promoter metal is 0.2-3 % by weight;
(b) solution impregnation with palladium source compound by the catalyst semi-finished product of preparation in step (a), then use hydrazine hydrate reduction, washing, dry and roasting afterwards, make palladium supported catalyst, the palladium metal content of this catalyst is 0.25-0.35 % by weight, and promoter metal content is 0.2-3 % by weight; And
(c) by step (b) gained palladium supported catalyst, in temperature, be optionally, that 100-150 ℃, Hydrogen Vapor Pressure are that 2.0-3.0MPa and hydrogen flowing quantity are to reduce under the condition of 2-15ml/min.g catalyst.
10. according to the method for claim 9, wherein based on the half-finished gross weight of catalyst, the calcium that the catalyst semi-finished product that obtain in step (a) contain 1-3 % by weight and the yttrium of 0-1 % by weight are as promoter metal.
11. according to the method for claim 9, and wherein 6-8h is carried out in the reduction in step (c).
12. according to the method for claim 9, and wherein promoter metal compound is the compound of calcium and yttrium, and/or palladium source compound is to be selected from one or more in lower group: palladium bichloride, palladium nitrate, palladium sulfate, tetranitro palladium acid sodium, H
2pdCl
4acylate with palladium.
13. according to the method for claim 12, and wherein the acylate of palladium is oxalic acid palladium.
14. according to the method for claim 9, and wherein the roasting in step (a) is carried out at the temperature of 500-600 ℃, and/or the roasting in step (b) is carried out at the temperature of 450-600 ℃; And/or the hydrazine hydrate in step (b) is with the aqueous solution or the alcoholic solution use of 30-40 % by weight.
15. according to the method for claim 14, and wherein 3-6 hour is carried out in the roasting in step (a); And/or 3-8 hour is carried out in the roasting in step (b); And/or the alcoholic solution relating in step (b) is ethanolic solution.
16. according to the method for any one in claim 9-15, and wherein magnesia-titania-alumina composite oxide carrier is according to the method preparation of any one in claim 4-8.
17. 1 kinds of methods of drippolene being carried out to selective hydrogenation, comprising:
(i) optionally, temperature be 100-150 ℃, Hydrogen Vapor Pressure be 2.0-3.0MPa and hydrogen flowing quantity be under the condition of 2-15ml/min.g catalyst reduction according to the catalyst described in any one in claim 1-3; And
(ii) in temperature, be that 50-60 ℃, pressure are that 2.6-3.0MPa, hydrogen to oil volume ratio are that 50:1-80:1 and liquid hourly space velocity (LHSV) are 8-12h
-1condition under hydrocrack gasoline.
18. methods according to claim 17, wherein 6-8 hour is carried out in the reduction in step (i).
19. methods according to claim 17, wherein said drippolene is drippolene C
5-C
9cut.
20. methods according to claim 17, wherein said drippolene is drippolene C
8and C
9heavy distillat.
21. according to the method described in any one in claim 17-20, and wherein said drippolene is that diene value is that 20-40g iodine/100g oil and bromine valency are the feedstock oil of 40-70g bromine/100g oil.
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| JP6401740B2 (en) * | 2016-06-13 | 2018-10-10 | 株式会社豊田中央研究所 | Exhaust gas purification catalyst and method for producing the same |
| JP7158953B2 (en) * | 2017-08-18 | 2022-10-24 | 中国石油化工股▲ふん▼有限公司 | Catalyst for producing light aromatic hydrocarbons from heavy aromatic hydrocarbons, production method and application thereof |
| CN110882703A (en) * | 2019-12-03 | 2020-03-17 | 北京赛诺时飞石化科技有限公司 | Alkaline earth metal-containing cycloparaffin dehydrogenation catalyst and preparation method thereof |
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| CN1884190A (en) * | 2006-06-27 | 2006-12-27 | 上海电力学院 | Method for preparing nano MgO-TiO2-Al2O3/mesoporous montmorillonite composites |
| US7232934B2 (en) * | 2003-09-19 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Hydrogenation of oxo aldehydes to oxo alcohols in the presence of a nickel-molybdenum catalyst |
| CN101818077A (en) * | 2009-02-27 | 2010-09-01 | 中国石油化工股份有限公司 | Selective hydrogenation method of highly unsaturated hydrocarbons in cracking gas |
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| US7232934B2 (en) * | 2003-09-19 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Hydrogenation of oxo aldehydes to oxo alcohols in the presence of a nickel-molybdenum catalyst |
| CN1884190A (en) * | 2006-06-27 | 2006-12-27 | 上海电力学院 | Method for preparing nano MgO-TiO2-Al2O3/mesoporous montmorillonite composites |
| CN101818077A (en) * | 2009-02-27 | 2010-09-01 | 中国石油化工股份有限公司 | Selective hydrogenation method of highly unsaturated hydrocarbons in cracking gas |
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