CN104941639A - Selective hydrogenation catalyst and preparation method and application thereof - Google Patents
Selective hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for selective hydrogenation of pyrolysis gasoline. The selective hydrogenation catalyst comprises an attapulgite-titanium oxide-aluminium oxide composite oxide as a carrier, and metal palladium active components and rare earth metal assistant metal which are loaded on the composite oxide carrier, wherein the content of metal palladium is 0.25-0.35wt%, the content of the assistant metal is 0-3wt%, and based on the content of aluminium oxide in the carrier, the content of attapulgite in the carrier is 0.1-3wt% and the content of titanium oxide in the carrier is 5-20wt%. The catalyst can be used for selective hydrogenation of pyrolysis gasoline and is high in low-temperature activity, high in selectivity, high in capacity of resisting impurities including As, S, O and N, large in glue containing amount and stable in activity under long-time running condition. In addition, the invention also relates to a preparation method of the catalyst and application of the catalyst in the selective hydrogenation of pyrolysis gasoline. Finally, the invention further relates to a composite oxide carrier preparation method by adopting a cocurrent flow coprecipitation method.
Description
Technical field
The present invention relates to a kind of petroleum hydrocarbon selec-tive hydrogenation catalyst, particularly drippolene C
5-C
9cut, especially C
8-C
9heavy distillat selec-tive hydrogenation catalyst.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, its output accounts for more than 50 % by weight of ethylene production capacity, and wherein arene content accounts for 40-80 % by weight, is therefore the main source of aromatic hydrocarbons.Industrial production cuts 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, after removing the organic compound such as monoene and sulphur, nitrogen, oxygen, and C
8cut is for the production of dimethylbenzene, and C
9cut is for the production of aromatic solvent naphtha.C
8cut also can only through a hydrogenation, and removing diolefin, 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 catalyst mainly Ni/Al
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 higher, make the very fast inactivation of catalyst, thus catalyst is had to frequent activation and regeneration.The Pd/Al of present industrial use
2o
3the catalyst the shortest regeneration period 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 catalyst regeneration cycle, thus extending catalyst service life, this is very important in the industrial production.
The open CN1443829A of Chinese patent application discloses a kind of drippolene one section of selective hydrogenation catalyst and method for making thereof, wherein the load capacity of active component Pd is the 0.05-0.4% of catalyst weight, and active component palladium is eggshell type distribution at carrier surface, 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, effectively can reduce the pressure drop of reaction bed, be conducive to reaction and remove heat, make bed temperature more even, be conducive to improving 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. 6576586 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst that can run under high-speed, wherein the load capacity of active component Pd is the 0.05-0.4% of catalyst weight, with 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 the Al with δ phase and α phase mixed phase
2o
3, wherein α phase Al
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.But, the low temperature active of this catalyst and selectively all to have much room for improvement.
The open CN1361231A of Chinese patent application discloses a kind of catalyst for selective hydrogenation of diolefin as, its carrier is the aluminium titanium composite oxide carrier 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 and occurs bimodal, load P d active component and optional IB and/or IA or IIA race metal, there is the advantages such as active high, selective height, sulfur resistive and arsenic ability are strong, but its low temperature active 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 catalyst, found that the support preparation method Pd obtained with adding auxiliary agent is catalyst based has better low temperature active, selective and stability by improving.The present invention is accomplished based on above discovery just.
Therefore, the object of this invention is to provide a kind of catalyst for selective hydrogenation of cracked gasoline newly, this catalyst has high, the anti-impurity ability of low temperature active and holds the advantage of high, the selective good and good stability of glue ability.
Another object of the present invention is to provide a kind of method preparing above-mentioned catalyst.
Another object of the present invention is to provide a kind of method of drippolene being carried out to selec-tive hydrogenation.
Another object of the present invention is to provide a kind of method preparing recessed soil-titanium dioxide-aluminum oxide composite oxides, and composite oxides prepared by the method are particularly suitable for the carrier being used as catalyst of the present invention.
First, the invention provides a kind of selective hydrogenation catalyst, comprising:
A) using recessed soil-titanium dioxide-aluminum oxide composite oxides as carrier, the content of described carrier concave soil is the 0.1-3 % by weight of alumina weight, and in described carrier, the content of titanium oxide is the 5-20 % by weight of alumina weight;
B) activity component metal palladium, the content of described Metal Palladium is the 0.25-0.35 % by weight of described total catalyst weight;
C) one or more are selected from the promoter of rare earth metal, and the content of described promoter is the 0-3 % by weight of described total catalyst weight.
In a preferred embodiment of catalyst of the present invention, catalyst of the present invention is loaded catalyst, active metal component palladium wherein and as the rare earth metal load of promoter on recessed soil-titanium dioxide-aluminum oxide composite oxide carrier.
In a preferred embodiment of catalyst of the present invention, the specific area of recessed soil-titanium dioxide-aluminum oxide composite oxide carrier is 80-180m
2/ g, most probable pore size is 9-19nm, and pore volume is 0.4-1.3ml/g, and crushing strength is greater than 18N/mm.In the present invention, crushing strength refers to side crush intensity, and it measures by intensity of pressure instrument; Specific area, most probable pore size and pore volume adopt nitrogen physisorption method to measure.
In a preferred embodiment of catalyst of the present invention, in recessed soil-titanium dioxide-aluminum oxide composite oxide carrier in the catalyst, the content of recessed soil is the weight 0.5-3 % by weight of aluminium oxide, and the content of titanium oxide is the weight 10-20 % by weight of aluminium oxide.
In a preferred embodiment of catalyst of the present invention, the content of described promoter is the 0-1 % by weight of described total catalyst weight.
In a preferred embodiment of catalyst of the present invention, described rare earth metal is selected from least one in lanthanum, cerium and praseodymium.
In a preferred embodiment of catalyst of the present invention, described promoter is selected from rare earth compound.Described rare earth compound can be selected from any organic and inorganic salts of rare earth metal.Such as can use the nitrate of rare earth metal, sulfate, chloride, acylate and/or acetylacetonate, preferred lanthanum nitrate, cerous nitrate and/or praseodymium nitrate.
Present invention also offers a kind of manufacture method of described selective hydrogenation catalyst, comprise the steps:
I) by recessed soil and hydrochloric acid solution mix and blend 10-24 hour recessed soil paste liquid, get upper strata suspension after leaving standstill, filtered by described upper strata suspension, the solid matter after filtering is dried, grind and to obtain the recessed soil after purifying;
Ii) recessed soil, titanium-containing compound and aluminum contained compound are mixed to form mixed solution by described component ratio, adopt co-precipitation method, in described mixed solution, add (NH
4)
2cO
3the aqueous solution or ammonia spirit mix and blend form precipitation;
Iii) gained precipitation in separating step (ii), by the precipitation of separation, dry and roasting, obtains recessed soil-titanium dioxide-aluminum oxide composite oxide carrier;
Iv) by described components b) and c) be carried on step I ii) on recessed soil-titanium dioxide-aluminum oxide composite oxide carrier of obtaining, thus obtain described catalyst.
In a preferred embodiment of manufacture method of the present invention, at step I i) in, in described recessed soil, titanium-containing compound and aluminum contained compound, add solvent form mixed solution, described solvent is selected from least one in water, methyl alcohol and ethanol.
In a preferred embodiment of manufacture method of the present invention, at least one that described titanium-containing compound is selected from the acetate of titanium, hydrochloride and nitrate or at least one be selected from tetraethyl titanate, metatitanic acid four n-propyl and tetra-n-butyl titanate; Described aluminum contained compound is selected from aluminum nitrate (as Al (NO
3)
39H
2o) at least one, in aluminium chloride, aluminum sulfate and their hydrate.
In a preferred embodiment of manufacture method of the present invention, step I v) in also comprise calcination steps, described roasting for carry out roasting 2-6 hour at 450-600 DEG C.
Be particularly suitable for being prepared by support preparation method of the present invention for recessed soil-titanium dioxide-aluminum oxide composite oxide carrier of the present invention.
In order to prepare recessed soil-titanium dioxide-aluminum oxide composite oxide carrier, first in step I) in the recessed soil of purifying, then at step I i) in preparation comprise the mixed solution of recessed soil, titanium compound and aluminium compound.The content of recessed soil, titanium compound and aluminium compound in this mixed solution should make: based on aluminium compound in the weight of aluminium oxide, the content of recessed soil is 0.1-3 % by weight, preferred 0.5-3 % by weight, and titanium compound in the content of titanium dioxide for 5-20 % by weight, preferred 10-20 % by weight.Preferably, based on aluminium compound in the weight of aluminium oxide, the content of recessed soil is 0.5-3 % by weight, and titanium compound in the content of titanium dioxide for 10-20 % by weight.In order to form described mixed solution, as solvent, water, methyl alcohol, ethanol or its mixture can be used as solvent, preferably using water as solvent.
Described titanium-containing compound, one or more titanium salts that can be selected from the acetate of titanium, hydrochloride and nitrate or at least one be selected from tetraethyl titanate, metatitanic acid four n-propyl and tetra-n-butyl titanate;
Described aluminum contained compound, can be selected from aluminum nitrate (as Al (NO
3)
39H
2o) at least one, in aluminium chloride, aluminum sulfate and their hydrate.
In above-mentioned promoter metal compound solution, forming the solvent that this solution uses can be such as water, nitric acid, hydrochloric acid, ammoniacal liquor or its mixture, can also be organic solvent, as ethanol, methyl alcohol, benzene, oxalic acid, acetic acid or its mixture etc., preferably use water as solvent.
In a preferred embodiment of support preparation method of the present invention, step I i) described in the preparation of mixed solution comprise:
(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) recessed soil is dissolved in deionized water or ethanol, is mixed with the recessed native solution S of 1-20g/L
aTP, and
(4) by solution S
ti, S
aland S
aTPmix according to required ratio, obtain step I i) described in mixed solution.
Obtained comprise the mixed solution of recessed soil, titanium compound and aluminium compound after, adopt co-precipitation method, at the temperature of 10-60 DEG C, under agitation while adding 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 step I i) in prepared mixed solution and (NH
4)
2cO
3the aqueous solution or ammonia spirit adopt and the mode that flows is fed in raw material, and are namely divided into two stock material streams and feed simultaneously, generate precipitation after two stock material stream contacts.The temperature of this co-precipitation reaction is generally 10-60 DEG C, and this such as by carrying out in water bath with thermostatic control.This co-precipitation needs to stir usually, such as mechanical agitation, magnetic agitation or ultrasonic agitation, and preferred mechanical stirs.(NH
4)
2cO
3the aqueous solution is that the aqueous solution of 0.1-2mol/L uses usually with concentration, and ammonia spirit is that the aqueous solution of 0.1-1mol/L uses usually with concentration.Preferably, the interpolation speed of mixed solution is (NH
4)
2cO
3the aqueous solution or ammonia spirit add the 0.1-2 of speed doubly.Such as, 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, advantageously can generate precipitation, the roasting subsequently of this precipitation can produce recessed soil-titanium dioxide-aluminum oxide composite oxides.Described pH value both can add (NH at the same time
4)
2cO
3producing when the aqueous solution or ammonia spirit and prepared mixed solution, also can be with ammoniacal liquor or (NH after adding prepared mixed solution
4)
2cO
3the aqueous solution regulates and obtains.
After obtaining precipitation, at step I ii) in, by the precipitation of separation, dry and roasting, obtains recessed soil-titanium dioxide-aluminum oxide composite oxide carrier.Described drying is carried out usually at 50-120 DEG C, and drying time is generally 1-24 hour.Subsequently, by the precipitation roasting of drying, this realizes advantageous by the roasting temperature in 450-600 DEG C, and roasting time is generally 2-6 hour, thus obtains recessed soil-titanium dioxide-aluminum oxide composite oxide carrier.Advantageously, by step I i) middle gained is deposited in ageing under room temperature, suction filtration and washing in its mother liquor, and then dry and roasting.The specific area of the recessed soil-titanium dioxide-aluminum oxide composite oxide carrier obtained after roasting is 80-180m
2/ g, most probable pore size is 9-19nm, and pore volume is 0.4-1.3ml/g.
In the manufacture method of selective hydrogenation catalyst of the present invention, step I v) specifically also comprise the steps:
I) by recessed soil-titanium dioxide-aluminum oxide composite oxide carrier dipping at least with the promoter metal compound solution of this composite oxide carrier pore volume equivalent, this promoter metal be selected from rare earth metal one or more, by the carrier drying through flooding and roasting, obtained catalyst semi-finished product, based on the half-finished gross weight of this catalyst, the content of promoter metal is 0-3 % by weight, and preferably these catalyst semi-finished product contain the cerium of 0-1 % by weight as promoter metal;
II) by step I) the middle catalyst semi-finished product solution impregnation of palladium source compound prepared, then use hydrazine hydrate (N
2h
4.H
2o) reduce, washing, afterwards dry and roasting, obtained palladium supported catalyst, the palladium metal content of this catalyst is 0.25-0.35 % by weight, and promoter metal content is 0-3 % by weight;
III) optionally, by Step II) gained palladium supported catalyst temperature be 100-150 DEG C, Hydrogen Vapor Pressure reduces under be 2.0-3.0MPa and hydrogen flowing quantity being the condition of 2-15ml/min.g, preferably reduces 6-8h.
Above-mentioned steps I) in roasting carry out at the temperature of 500-600 DEG C, preferably carry out 3-6 hour, and/or step I i) in roasting carry out at the temperature of 450-600 DEG C, preferably carry out 3-8 hour.
Above-mentioned steps II) in palladium source compound be selected from lower group one or more: palladium bichloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, the acid of tetranitro palladium sodium, H
2pdCl
4with the acylate of palladium.
In order to carry out step I) in dipping, usually recessed native titanium dioxide-aluminum oxide composite oxide carrier is immersed a period of time, such as 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 immersion, leaching removes unnecessary maceration extract, and by the carrier drying through dipping of gained, this keeps a period of time to realize usually at the temperature of 100-150 DEG C, such as, usually keep realizing for 8-12 hour.Then, by the composite oxide carrier roasting of drying, promoter metal compound to be transformed into the oxide of promoter metal, this keeps a period of time to realize usually at the temperature of 500-600, such as, usually keep realizing for 3-6 hour.After roasting, i.e. obtained catalyst semi-finished product.After obtaining catalyst semi-finished product as mentioned above, carry out Step II as above), namely, by step I) in the catalyst semi-finished product solution impregnation of palladium source compound of preparation, then dry and roasting, obtained palladium supported catalyst, the palladium metal content of this catalyst is 0.25-0.35 % by weight, and promoter metal content is 0-3 % by weight.In Step II) in the solution of palladium source compound that uses, the solvent used for the formation of this solution can be water, methyl alcohol, ethanol or its mixture, preferably uses water as solvent.As above-mentioned steps II) the middle palladium source compound used, any one can be used to be suitable for preparing the palladium compound of palladium catalyst, as palladium bichloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, the acid of tetranitro palladium sodium, H
2pdCl
4, palladium acylate (as oxalic acid palladium) or its mixture etc.These palladium source compounds are preferably that the solution (preferred aqueous solutions) of 0.15-0.75g/ml, more preferably 0.2-0.7g/ml uses with concentration.The consumption of palladium source compound solution answers submergence step I) the middle catalyst semi-finished product prepared, preferably its consumption is the solution that every gram of catalyst semi-finished product use 0.5-3ml palladium source compound.Step I) in the catalyst semi-finished product of preparation usually use the solution impregnation 0.5-2 hour of palladium source compound.
At above-mentioned steps II) in, after dipping, product is dry at 100-150 DEG C, and this carries out 4-8 hour usually.Then, by the roasting at 450-600 DEG C of the product of drying, this carries out 3-8 hour usually, obtained palladium supported catalyst.
In Step II) after, by Step II) in obtain palladium supported catalyst hydrogen reducing activate.As selection, Step II) in the palladium supported catalyst that obtains also can for reactivation during drippolene hydrogenation.That is, in the method preparing catalyst of the present invention, Step II I) not the step that must carry out.
If carry out Step II I), then Step II I) in palladium supported catalyst activation usually by its temperature be 100-150 DEG C, Hydrogen Vapor Pressure also carried out under be 2.0-3.0MPa and hydrogen flowing quantity being the condition of 2-15ml/min.g catalyst originally, preferably reduced 6-8h.
Present invention also offers and a kind ofly use described selective hydrogenation catalyst to carry out the method for selec-tive hydrogenation to drippolene, under being included in the existence of described catalyst, selec-tive hydrogenation is carried out to described drippolene.
In a preferred embodiment of the present invention, described method also comprises: before the described catalyst of use, temperature be 100-150 DEG C, Hydrogen Vapor Pressure reduces described catalyst under be 2.0-3.0MPa and hydrogen flowing quantity being the condition of 2-15ml/min.g.
In a preferred embodiment of the present invention, the temperature of described selec-tive hydrogenation is 50-60 DEG C, pressure is 2.6-3.0MPa, hydrogen to oil volume ratio be 50:1-80:1 and liquid hourly space velocity (LHSV) is 8-12h
-1.
The preferred drippolene C of described drippolene
5-C
9cut, especially C
8and C
9double distilled.
In selec-tive hydrogenation method of the present invention, described drippolene to be diene value be 20-40g iodine/100g oil and bromine valency are the feedstock oil of 40-70g bromine/100g oil.
Catalyst of the present invention is particularly suitable for drippolene C
5-C
9cut, especially C
8and C
9the selec-tive hydrogenation of heavy distillat.For this selec-tive hydrogenation, first optionally catalyst hydrogen reducing of the present invention is activated.If carry out, this reduction activation by by catalyst of the present invention temperature be 100-150 DEG C, Hydrogen Vapor Pressure 2.0-3.0MPa and hydrogen flowing quantity reduce a period of time and carry out, preferably reduction 6-8 hour under being the condition of 2-15ml/min.g catalyst.Should be understood that, if in catalyst preparation process, that catalyst reduction is not active, then drippolene is carried out in the method for selective hydrogenation of the present invention, must reduction activation be carried out.Then, temperature be 50-60 DEG C, pressure is 2.6-3.0MPa, hydrogen to oil volume ratio be 50:1-80:1 and liquid hourly space velocity (LHSV) is 8-12h
-1condition under hydrogenated pyrolysis gasoline.
Beneficial effect of the present invention:
Catalyst of the present invention in preparation process, adds rare earth compound as auxiliary agent, obtains after multistep dipping and high-temperature roasting.Compare with prior art, it has following outstanding advantages and effect:
1. high, the selective height of low temperature hydrogenation activity that has of catalyst of the present invention.
2. catalyst of the present invention holds glue and the advantage such as anticol performance is good, hydrogenation activity is stablized, and life cycle is long.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail, but scope of the present invention is not limited to following examples.
Catalyst Preparation Example
Embodiment 1
Step 1
(1) TiCl is used
4with the TiCl of deionized water preparation 0.25mol/L
4the aqueous solution;
(2) Al (NO is used
3)
39H
2o crystal and the aluminum nitrate aqueous solution removing dried up preparation 1.55mol/L;
(3) use recessed soil and remove the dried up recessed native aqueous solution preparing 10g/L;
(4) according to based on aluminum nitrate with Al
2o
3the weight TiCl of meter
4with TiO
2meter content be 20 % by weight and recessed native content be 1 % by weight amount, by solution A, B and C mixing, obtain containing recessed soil, Ti and Al mixed solution;
(5) adopt co-precipitation method, in the water bath with thermostatic control of 40 DEG C, drip (the NH of 0.5mol/L under magnetic stirring simultaneously
4)
2cO
3the aqueous solution and the mixed solution containing recessed soil, Ti and Al prepared, wherein the rate of addition of mixed solution is 60 droplets/minute, (NH
4)
2cO
3the rate of addition of the aqueous solution is 30 droplets/minute; After being added dropwise to complete, regulating the acid-base value of reactant mixture to pH=8 with the ammoniacal liquor of 0.5mol/L, forming precipitation;
(6) to be deposited in its mother liquor ageing 12h, suction filtration under room temperature by gained, to spend deionized water to without Cl
-, then put into baking oven at 100 DEG C dry 12 hours, 500 DEG C of roasting temperatures 4 hours, obtain recessed soil-titania-alumina composite oxide carrier.In this carrier, based on the weight of aluminium oxide, the content of recessed soil is 1 % by weight, TiO
2content be 20 % by weight; And the specific area of this carrier is 128m
2/ g, most probable pore size is 18nm, and pore volume is 0.52ml/g.
Step 2
Get the recessed soil-titania-alumina composite oxide carrier of preparation in 97g step 1, add wherein containing cerous nitrate 0.2mol/L aqueous solution 90ml as maceration extract, stir 15 minutes, leaching removes unnecessary maceration extract, then at 120 DEG C of dry 10h, at 550 DEG C of roasting 4h, the obtained catalyst semi-finished product containing cerium.
Step 3
It is in the palladium chloride aqueous solution of 0.509g/ml that the catalyst semi-finished product of preparation in 100g step 2 are immersed 85ml concentration, takes out, drain after 1 hour, at 120 DEG C dry 6 hours, then roasting 4 hours at 480 DEG C, obtained palladium-based catalyst 1.
The palladium content of palladium-based catalyst 1 is 0.3 % by weight, and cerium content is 0.3 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the content of recessed soil is 1 % by weight, TiO based on the weight of aluminium oxide
2content be 20 % by weight based on the weight of aluminium oxide.
Embodiment 2
Repeat the step 1-3 of embodiment 1, unlike: 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 20 % by weight, and the content of recessed soil is the amount of 3 % by weight, by solution A, B and C mixing, obtains the mixed solution containing recessed soil, Ti and Al.
As a result, in recessed soil-titania-alumina composite oxide carrier that step 1 obtains, based on the weight of aluminium oxide, the content of recessed soil is 3 % by weight, TiO
2content be 20 % by weight; And the specific area of this carrier is 122m
2/ g, most probable pore size is 17nm, and pore volume is 0.50ml/g.
As a result, palladium-based catalyst 2 is obtained through step 3.The palladium content of palladium-based catalyst 2 is 0.3 % by weight, and cerium content is 0.3 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the content of recessed soil is 3 % by weight, TiO based on the weight of aluminium oxide
2content be 20 % by weight based on the weight of aluminium oxide.
Embodiment 3
Repeat the step 1-3 of embodiment 1, unlike: the lanthanum nitrate aqueous solution maceration extract of the dipping complex carrier used in step 2 being changed the 0.2mol/L making 90ml.
As a result, final acquisition palladium-based catalyst 3.The palladium content of palladium-based catalyst 3 is 0.3 % by weight, and lanthanum content is 0.3 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the content of recessed soil is 1 % by weight, TiO based on the weight of aluminium oxide
2content be 20 % by weight based on the weight of aluminium oxide; And the specific area of this carrier is 128m
2/ g, most probable pore size is 18nm, and pore volume is 0.52ml/g.
Embodiment 4
Repeat the step 1-3 of embodiment 1, unlike: the praseodymium nitrate aqueous solution maceration extract of the dipping complex carrier used in step 2 being changed the 0.2mol/L making 90ml.
As a result, obtain the catalyst semi-finished product containing praseodymium in step 2, and obtain palladium-based catalyst 4 through step 3.The palladium content of palladium-based catalyst 4 is 0.3 % by weight, and praseodymium content is 0.3 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the content of recessed soil is 1 % by weight, TiO based on the weight of aluminium oxide
2content be 20 % by weight based on the weight of aluminium oxide; And the specific area of this carrier is 128m
2/ g, most probable pore size is 18nm, and pore volume is 0.52ml/g.
Embodiment 5
Repeat the step 1-3 of embodiment 1, unlike: the maceration extract of the dipping complex carrier used in step 2 is changed the mixed aqueous solution 90ml done containing cerous nitrate 0.13mol/L.
As a result, obtain the catalyst semi-finished product containing cerium in step 2, and obtain palladium-based catalyst 5 through step 3.The palladium content of palladium-based catalyst 5 is 0.3 % by weight, and cerium content is 0.2 % by weight, and crushing strength is 21N/mm; In the carrier of this catalyst, the content of recessed soil is 1 % by weight, TiO based on the weight of aluminium oxide
2content be 20 % by weight based on the weight of aluminium oxide; And the specific area of this carrier is 128m
2/ g, most probable pore size is 18nm, and pore volume is 0.52ml/g.
Comparative example 1
Repeat the step 1-3 of embodiment 1, unlike: the maceration extract of the dipping complex carrier used in step 2 is changed and makes 90ml deionized water.
As a result, the catalyst semi-finished product obtained in step 2 not containing rare earth metal, and obtain comparative catalyst 1 through step 3.The palladium content of comparative catalyst 1 is 0.3 % by weight, crushing strength is 21N/mm; In the carrier of this catalyst, the content of recessed soil is 1 % by weight, TiO based on the weight of aluminium oxide
2content be 20 % by weight based on the weight of aluminium oxide; And the specific area of this carrier is 128m
2/ g, most probable pore size is 18nm, and pore volume is 0.52ml/g.
Comparative example 2
Repeat the step 1-3 of embodiment 1, unlike: the sub-step (3) omitting step 1, result, obtains titania-alumina carrier in step 1; The specific area of this carrier is 120m
2/ g, most probable pore size is 16nm, and pore volume is 0.49ml/g.
As a result, the catalyst semi-finished product containing cerium are obtained through step 2.
As a result, comparative catalyst 2 is obtained through step 3.The palladium content of comparative catalyst 2 is 0.3 % by weight, and cerium content is 0.3 % by weight, and crushing strength is 21N/mm.
Comparative example 3
Repeat the step 1-3 of embodiment 1, unlike: omit the sub-step (1) of step 1, (3) and (4), result, obtains alumina support in step 1; The specific area of this carrier is 122m
2/ g, most probable pore size is 17nm, and pore volume is 0.50ml/g.
As a result, the catalyst semi-finished product containing cerium are obtained through step 2.
As a result, comparative catalyst 3 is obtained through step 3.The palladium content of comparative catalyst 3 is 0.3 % by weight, and cerium content is 0.3 % by weight, and crushing strength is 21N/mm.
The content of palladium-based catalyst 1-5 and comparative catalyst 1-3 rare earth metal auxiliary agent is separately in table 1.
Table 1
Embodiment 9
The present embodiment illustrates that the catalyst of embodiment 1-5 and comparative example 1-3 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, internal diameter 26mm, and loaded catalyst is 100ml.
The catalyst 1-5 that Example 1-5 and comparative example 1-3 obtains and each 100ml of comparative catalyst 1-3 is loaded in the reaction tube of hydrogenation evaluating apparatus respectively, be 2.8MPa at Hydrogen Vapor Pressure, temperature is 110 DEG C and hydrogen flowing quantity is reduce 8 hours under the condition of 4ml/min.g catalyst.Then lower the temperature, be 2.8Mpa at Hydrogen Vapor Pressure afterwards, reaction temperature is 50 DEG C, and hydrogen to oil volume ratio is 80:1, and total liquid hourly space velocity (LHSV) is 12h
-1condition under pass into that diene value is 20.27g iodine/100g oil, bromine valency is 40.36g bromine/100g oil, gum level be 232mg/100ml oil, nitrogen content is 3.4mg/100ml oil, oxide content is 2.19g/100ml oil, the drippolene C of sulfur content to be 110ppm and arsenic content be 180ppb
8cut, hydrogenation the results are shown in Table 2.
Table 2
Note: * bromine valency is the index weighing unsaturated hydrocarbons content in drippolene.Bromine valency is higher, then in interpret sample, unsaturated hydrocarbons content is higher, and namely degree of unsaturation is higher.
Containing the diene such as styrene and conjugated diene in drippolene, the existence of diene can have a strong impact on the stability of drippolene, so diene value is larger, unstability got over by drippolene.
As can be seen from Table 2 when containing rare-earth additive and recessed soil in catalyst, the catalytic effect of catalyst is all fine.Different rare-earth additive (catalyst 1,3 and 4), different rare-earth additive content (catalyst 1 and 5), the catalytic effect impact of different recessed native content (catalyst 1 and 2) on catalyst is little.
When not containing rare-earth additive and recessed soil (comparative catalyst 1,2 and 3) in catalyst, the catalytic performance of catalyst declines rapidly.
Embodiment 10
The palladium-based catalyst 1100ml that Example 1 is obtained, 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, be 2.8MPa at Hydrogen Vapor Pressure, temperature is 110 DEG C and hydrogen flowing quantity is reduce 8 hours under the condition of 4ml/min.g catalyst.Then lower the temperature, be 2.8MPa at Hydrogen Vapor Pressure afterwards, reaction temperature is 50 DEG C, and hydrogen to oil volume ratio is 80:1, and feeding liquid hourly space velocity is 8h
-1condition under pass into that diene value is 20.27g iodine/100g oil, bromine valency is 40.36g bromine/100g oil, gum level be 232mg/100ml oil, nitrogen content is 3.4mg/100ml oil, oxide content is 2.19g/100ml oil, the drippolene C of sulfur content to be 110ppm and arsenic content be 180ppb
8cut, when fresh feed liquid hourly space velocity (LHSV) is 2.0
-1, in 1000 hours reaction time, hydrogenation result is as following table 3.
Table 3
According to table 3 column data, palladium-based catalyst 1 has good stability.
Claims (13)
1. a selective hydrogenation catalyst, comprising:
A) using recessed soil-titanium dioxide-aluminum oxide composite oxides as carrier, the content of described carrier concave soil is the 0.1-3 % by weight of alumina weight, and in described carrier, the content of titanium oxide is the 5-20 % by weight of alumina weight;
B) activity component metal palladium, the content of described Metal Palladium is the 0.25-0.35 % by weight of described total catalyst weight;
C) at least one is selected from the promoter based on rare earth metal, and the content of described promoter is the 0-3 % by weight of described total catalyst weight.
2. catalyst according to claim 1, is characterized in that, the specific area of recessed soil-titanium dioxide-aluminum oxide composite oxide carrier is 80-180m
2/ g, most probable pore size is 9-19nm, and pore volume is 0.4-1.3ml/g, and crushing strength is greater than 18N/mm.
3. catalyst according to claim 1 and 2, it is characterized in that, in recessed soil-titanium dioxide-aluminum oxide composite oxide carrier in the catalyst, the content of recessed soil is the weight 0.5-3 % by weight of aluminium oxide, and the content of titanium oxide is the weight 10-20 % by weight of aluminium oxide.
4. the catalyst according to any one of claim 1-3, is characterized in that, the content of described promoter is the 0-1 % by weight of described total catalyst weight.
5. the catalyst according to any one of claim 1-4, is characterized in that, described rare earth metal is selected from least one in lanthanum, cerium and praseodymium.
6. the catalyst according to any one of claim 1-5, it is characterized in that, described promoter is selected from least one in the nitrate of rare earth metal, sulfate, chloride, acylate and acetylacetonate, at least one in preferred lanthanum nitrate, cerous nitrate and praseodymium nitrate.
7. a manufacture method for the selective hydrogenation catalyst according to any one of claim 1-6, comprises the steps:
I) by recessed soil and hydrochloric acid solution mix and blend 10-24 hour recessed soil paste liquid, get upper strata suspension after leaving standstill, filtered by described upper strata suspension, the solid matter after filtering is dried, grind and to obtain the recessed soil after purifying;
Ii) recessed soil, titanium-containing compound and aluminum contained compound are mixed to get mixed solution by described component ratio, adopt co-precipitation method, in described mixed solution, add (NH
4)
2cO
3the aqueous solution or ammonia spirit mix and blend form precipitation;
Iii) gained precipitation in separating step (ii), by the precipitation of separation, dry and roasting, obtains recessed soil-titanium dioxide-aluminum oxide composite oxide carrier;
Iv) by described components b) and c) be carried on step I ii) on recessed soil-titanium dioxide-aluminum oxide composite oxide carrier of obtaining, thus obtain described catalyst.
8. method according to claim 7, is characterized in that, at step I i) in, in described recessed soil, titanium-containing compound and aluminum contained compound, add solvent form mixed solution, described solvent is selected from least one in water, methyl alcohol and ethanol.
9. the method according to claim 7 or 8, is characterized in that, at least one that described titanium-containing compound is selected from the acetate of titanium, hydrochloride and nitrate or at least one be selected from tetraethyl titanate, metatitanic acid four n-propyl and tetra-n-butyl titanate; Described aluminum contained compound is selected from least one in aluminum nitrate, aluminium chloride, aluminum sulfate and their hydrate.
10. use the selective hydrogenation catalyst according to any one of claim 1-6 drippolene to be carried out to a method for selec-tive hydrogenation, under being included in the existence of described catalyst, selec-tive hydrogenation is carried out to described drippolene.
11. methods according to claim 10, it is characterized in that, described method also comprises: before the described catalyst of use, temperature be 100-150 DEG C, Hydrogen Vapor Pressure reduces described catalyst under be 2.0-3.0MPa and hydrogen flowing quantity being the condition of 2-15ml/min.g.
12. methods according to claim 10 or 11, is characterized in that, the temperature of described selec-tive hydrogenation is 50-60 DEG C, pressure is 2.6-3.0MPa, hydrogen to oil volume ratio be 50:1-80:1 and liquid hourly space velocity (LHSV) is 8-12h
-1.
13. methods according to any one of claim 10-12, it is characterized in that, described drippolene is drippolene C
5-C
9cut, preferred described drippolene to be diene value be 20-40g iodine/100g oil and bromine valency are the feedstock oil of 40-70g bromine/100g oil.
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| CN106362725A (en) * | 2016-08-26 | 2017-02-01 | 安徽金邦医药化工有限公司 | Solid catalyst and application thereof to preparing methyl formate isothiocyanate through catalysis |
| CN108499559A (en) * | 2017-02-28 | 2018-09-07 | 中国石油化工股份有限公司 | A kind of catalyst for preparing isobutene through dehydrogenation of iso-butane, preparation method and application |
| CN108855090A (en) * | 2017-05-08 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of ethylene glycol hydrogenation catalyst and preparation method thereof |
| CN113694944A (en) * | 2020-05-20 | 2021-11-26 | 中国石油化工股份有限公司 | Palladium-based selective hydrogenation catalyst for pyrolysis gasoline and preparation method and application thereof |
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| CN102732294A (en) * | 2011-04-11 | 2012-10-17 | 中国石油化工股份有限公司 | Method for selective hydrogenation of cracked gasoline or its fractions through adopting Pd-Ag/Al2O3-TiO2 catalyst |
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| CN113694944A (en) * | 2020-05-20 | 2021-11-26 | 中国石油化工股份有限公司 | Palladium-based selective hydrogenation catalyst for pyrolysis gasoline and preparation method and application thereof |
| CN115254119A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Coal tar hydrogenation catalyst, and preparation method and application thereof |
| CN115254082A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN115254119B (en) * | 2021-04-29 | 2024-03-26 | 中国石油化工股份有限公司 | Coal tar hydrogenation catalyst and preparation method and application thereof |
| CN115254082B (en) * | 2021-04-29 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst carrier, preparation method thereof, catalyst, preparation method thereof and application of catalyst |
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