CN104941639B - A kind of selective hydrogenation catalyst and its preparation method and application - Google Patents
A kind of selective hydrogenation catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for selective hydrogenation of cracked gasoline, it includes the recessed native titanium oxide alumina composite oxides as carrier, and it is carried on Metal Palladium active component and rare earth metal promoter metal on the composite oxide carrier, wherein metal palladium content is 0.25 0.35 weight %, promoter metal content is 03 weight %, and the content based on the recessed soil of aluminium oxide in carrier is 0.1 3 weight % and the content of titanium oxide is 5 20 weight %.The catalyst can be used for selective hydrogenation of cracked gasoline, and low temperature active is high, and high selectivity, anti-As, S, O, N impurity ability is strong, and charging capacity is greatly and activity stabilized under long-term operation.Moreover, it relates to the preparation of the catalyst and the application in hydrocracking gasoline is selected.Finally, the invention further relates to a kind of methods using composite oxide carrier used in the preparation of co-precipitation method.
Description
Technical field
The present invention relates to a kind of petroleum hydrocarbons to select catalyst for hydrogenation, particularly drippolene C5-C9Fraction, especially
C8-C9Double distilled component selections catalyst for hydrogenation.The invention further relates to the preparation method and applications of the catalyst.
Background technology
Drippolene C5-C9Fraction is the by-product of ethylene industry, according to the difference of cracking stock and cracking severity, production
Amount accounts for about more than the 50 weight % of ethylene production capacity, and wherein arene content accounts for 40-80 weight %, therefore is the main next of aromatic hydrocarbons
Source.C is cut in industrial production8And C9Fraction 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 compounds such as monoene and sulphur, nitrogen, oxygen, C8Fraction
For producing dimethylbenzene, and C9Fraction is used to produce aromatic solvent naphtha.C8Fraction can also remove diolefin, protect only through once adding hydrogen
Most of monoene is stayed, obtains stable motor petrol adulterant or the higher motor petrol of octane number.
Industrial drippolene C at present5-C9Fraction selective hydrogenation is mainly Ni/Al with catalyst2O3Or Pd/Al2O3,
There is Pd-Cr/Al2O3Bimetallic catalyst.Due to drippolene C8And C9In heavy distillat the impurity such as As, S, O, N and gum level compared with
Height makes catalyst inactivate quickly, thus catalyst infrequently must not be activated and be regenerated.The Pd/Al industrially used now2O3It urges
The agent most short regeneration period is 7 days.Therefore, it is intended that there is hydrogenation catalyst higher low temperature active, higher anti-impurity to be poisoned
Ability and appropriate appearance glue ability, to increase catalyst regeneration cycle, so as to extend catalyst service life, this is in industrial production
In it is particularly significant.
Chinese patent application discloses CN1443829A and discloses a kind of one section of selective hydrogenation catalyst of drippolene and its system
Method, the wherein load capacity of active component Pd are the 0.05-0.4% of catalyst weight, and active component palladium is in egg in carrier surface
Shell mould is distributed, shell thickness 0.03-0.09mm；Its carrier be alumina support, crystalline phase be δ phases, the Kong Rongwei 0.6- of carrier
0.9ml/g, specific surface area 140-170m2/g.The catalyst, can be effective compared with the granular catalyst industrially used at present
The pressure drop of reaction bed is reduced, is conducive to reaction and removes heat, make bed temperature more uniform, is conducive to improve the selection of purpose product
Property, high-speed operating is adapted to, and with preferable stability, but its activity and selectivity still leaves some room for improvement.
United States Patent (USP) US6576586 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst that can be run under high-speed,
Wherein the load capacity of active component Pd is the 0.05-0.4% of catalyst weight, using alkali metal or/and alkaline-earth metal as auxiliary agent,
Load capacity is the 0.05-2.0% of catalyst weight, and carrier is the Al that phase is mixed with δ phases and α2O3, wherein α phases Al2O3It accounts for
0.5-5wt%, the Kong Rongwei 0.5-0.9ml/g of carrier, aperture are distributed in 4-20nm, specific surface area 70-140m mostly2/g.So
And the low temperature active of the catalyst and selectivity have much room for improvement.
Chinese patent application discloses CN1361231A and discloses a kind of catalyst for selective hydrogenation of diolefin as, carrier
For the aluminium titanium composite oxide carrier prepared using chemical coprecipitation, the wherein weight percent content of aluminium oxide is 1-99%,
Carrier aperture, which is distributed at 50nm and 1000nm, to be occurred bimodal, loads Pd active components and optional IB and/or IA or Group IIA
The advantages that metal, active height, high selectivity, strong sulfur resistive and arsenic ability, but its low temperature active still has much room for improvement.
Invention content
In view of above-mentioned prior art situation, the present inventor has carried out catalyst for selective hydrogenation of cracked gasoline extensively
General in-depth study, as a result, it has been found that by improving Pd bases catalyst made from support preparation method and addition auxiliary agent with better
Low temperature active, selectivity and stability.The present invention has found to be accomplished more than being based on.
It is therefore an object of the present invention to provide a kind of new catalyst for selective hydrogenation of cracked gasoline, the catalyst
Have the advantages that low temperature active height, anti-impurity ability and appearance glue ability are high, selectivity is good and stability is good.
It is a further object of the present invention to provide a kind of methods for preparing above-mentioned catalyst.
Another object of the present invention is to provide a kind of method that selection plus hydrogen are carried out to drippolene.
It is yet another object of the invention to provide a kind of method for preparing recessed soil-titanium dioxide-aluminum oxide composite oxides, the party
Composite oxides prepared by method are particularly suited for use as the carrier of catalyst of the present invention.
First, the present invention provides a kind of selective hydrogenation catalyst, including：
a）Using recessed soil-titanium dioxide-aluminum oxide composite oxides as carrier, the content of the carrier concave soil is aluminium oxide
The 0.1-3 weight % of weight, the content of titanium oxide is the 5-20 weight % of alumina weight in the carrier；
b）Activity component metal palladium, the content of the Metal Palladium are the 0.25-0.35 weight % of the total catalyst weight；
c）One or more accelerating agents selected from rare earth metal, the content of the accelerating agent is the total catalyst weight
0-3 weight %.
In a preferred embodiment of catalyst of the present invention, catalyst of the present invention is loaded catalyst,
In active metal component palladium and rare earth metal as accelerating agent be supported on recessed soil-titanium dioxide-aluminum oxide composite oxides and carry
On body.
In a preferred embodiment of catalyst of the present invention, recessed soil-titanium dioxide-aluminum oxide composite oxides carry
The specific surface area of body is 80-180m2/ g, most probable pore size 9-19nm, Kong Rongwei 0.4-1.3ml/g, and crushing strength is big
In 18N/mm.In the present invention, crushing strength refers to side crush intensity, can be measured by intensity of pressure instrument；Specific surface
Product, most probable pore size and Kong Rong are measured using nitrogen physisorption method.
In a preferred embodiment of catalyst of the present invention, recessed soil-titanium oxide-oxygen in the catalyst
Change in aluminium composite oxide carrier, the content of recessed soil is the weight 0.5-3 weight % of aluminium oxide, and the content of titanium oxide is aluminium oxide
Weight 10-20 weight %.
In a preferred embodiment of catalyst of the present invention, the content of the accelerating agent is total for the catalyst
The 0-1 weight % of weight.
In a preferred embodiment of catalyst of the present invention, the rare earth metal is in lanthanum, cerium and praseodymium
It is at least one.
In a preferred embodiment of catalyst of the present invention, the accelerating agent is selected from rare earth compound.
The rare earth compound may be selected from any organic and inorganic salts of rare earth metal.Such as the nitric acid of rare earth metal can be used
Salt, sulfate, chloride, acylate and/or acetylacetonate, preferably lanthanum nitrate, cerous nitrate and/or praseodymium nitrate.
The present invention also provides a kind of manufacturing methods of the selective hydrogenation catalyst, include the following steps：
I) recessed soil paste liquid is mixed 10-24 hours to obtain in recessed soil and hydrochloric acid solution, upper strata suspension is taken after standing, by institute
It states upper strata suspension to be filtered, the recessed soil dry the solid matter after filtering, ground after purification；
Ii recessed soil, titanium-containing compound and aluminum contained compound) are mixed to form mixed solution by the component ratio, using simultaneously
Coprecipitation is flowed, (NH is added in the mixed solution4)2CO3Aqueous solution or ammonia spirit are mixed to form precipitation；
Iii) gained precipitates in separating step (ii), by the precipitation drying and roasting of separation, obtains recessed soil-titanium oxide-oxygen
Change aluminium composite oxide carrier；
Iv) by the component b）And c）It is carried on step iii) obtained recessed soil-titanium dioxide-aluminum oxide composite oxides carry
On body, so as to obtain the catalyst.
In a preferred embodiment of the manufacturing method of the present invention, in step ii）In, in the recessed soil, containing titanizing
It closes and solvent formation mixed solution is added in object and aluminum contained compound, the solvent is selected from least one of water, methanol and ethyl alcohol.
In a preferred embodiment of the manufacturing method of the present invention, acetate of the titanium-containing compound selected from titanium,
Hydrochloride and nitrate at least one or in tetraethyl titanate, four n-propyl of metatitanic acid and tetra-n-butyl titanate at least one
Kind；The aluminum contained compound is selected from aluminum nitrate (such as Al (NO3)3·9H2O), in aluminium chloride, aluminum sulfate and their hydrate
At least one.
In a preferred embodiment of the manufacturing method of the present invention, in step iv）In further include calcination steps, it is described
It is roasted to and roasting 2-6 hours is carried out at 450-600 DEG C.
It is particularly suitable for for recessed soil-titanium dioxide-aluminum oxide composite oxide carrier of the present invention through carrier of the invention
It is prepared by preparation method.
In order to prepare recessed soil-titanium dioxide-aluminum oxide composite oxide carrier, the recessed soil of purifying first in step i), then
In step ii) in prepare the mixed solution comprising recessed soil, titanium compound and aluminium compound.Recessed soil in the mixed solution, titanizing
Closing the content of object and aluminium compound should cause：Weight based on aluminium compound in terms of aluminium oxide, the content of recessed soil is 0.1-3 weights
%, preferably 0.5-3 weight % are measured, and titanium compound is using the content that titanium dioxide is counted as 5-20 weight %, preferably 10-20 weight %.
Preferably, the weight based on aluminium compound in terms of aluminium oxide, the content of recessed soil is 0.5-3 weight %, and titanium compound is with two
The content of titanium oxide meter is 10-20 weight %.In order to form the mixed solution, as solvent, water, methanol, ethyl alcohol can be used
Or its mixture as solvent, it is preferable to use water is as solvent.
The titanium-containing compound can be selected from the acetate of titanium, one or more titanium salts of hydrochloride and nitrate or choosing
From at least one of tetraethyl titanate, four n-propyl of metatitanic acid and tetra-n-butyl titanate；
The aluminum contained compound can be selected from aluminum nitrate (such as Al (NO3)3·9H2O), aluminium chloride, aluminum sulfate and they
At least one of hydrate.
In above-mentioned promoter metal compound solution, it for example can be water, nitric acid, salt to form solvent used in the solution
Acid, ammonium hydroxide or its mixture, can also be organic solvent, such as ethyl alcohol, methanol, benzene, oxalic acid, acetic acid or its mixture, preferably
Using water as solvent.
In a preferred embodiment of support preparation method of the present invention, step ii) described in mixed solution preparation
Including：
(1) titanium compound is dissolved in deionized water or ethyl alcohol, is configured to the compound titanium solution S of 0.1-1mol/LTi,
(2) aluminium compound is dissolved in deionized water or ethyl alcohol, is configured to the aluminum compound solution S of 1-5mol/LAl,
(3) recessed soil is dissolved in deionized water or ethyl alcohol, is configured to the recessed native solution S of 1-20g/LATPAnd
(4) by solution STi、SAlAnd SATPAccording to required ratio mix, obtain step ii) described in mixed solution.
After the mixed solution comprising recessed soil, titanium compound and aluminium compound is made, using co-precipitation method, in 10-
At a temperature of 60 DEG C, (NH is added in while prepared mixed solution is added under stiring4)2CO3Aqueous solution or ammonium hydroxide are molten
Liquid, with ammonium hydroxide or (NH4)2CO3Aqueous solution adjusts reaction mixture to pH=7-9, forms precipitation.
In the present invention, so-called co-precipitation method refers to step ii) in prepared mixed solution and (NH4)2CO3
Aqueous solution or ammonia spirit are fed using cocurrent mode, that is, are divided into two stock material streams and are fed simultaneously, and it is heavy to be generated after the contact of two stock material streams
It forms sediment.The temperature of co-precipitation reaction is usually 10-60 DEG C, this in water bath with thermostatic control for example by carrying out.The cocurrent is coprecipitated
It forms sediment and usually requires stirring, such as mechanical agitation, magnetic agitation or ultrasonic agitation, preferably mechanical agitation.(NH4)2CO3Aqueous solution leads to
It is often used with the aqueous solution of a concentration of 0.1-2mol/L, ammonia spirit is usually used with the aqueous solution of a concentration of 0.1-1mol/L.
Preferably, the adding speed of mixed solution is (NH4)2CO30.1-2 times of aqueous solution or ammonia spirit adding speed.For example,
The adding speed of mixed solution be 60-80 drops/minute, (NH4)2CO3The rate of addition of aqueous solution or ammonia spirit for 30-40 drops/
Minute.When reaction mixture pH value is 7-9, precipitation can be advantageously generated, then roasting can generate recessed soil-oxidation to the precipitation
Titanium-alumina composite oxide.The pH value can both add (NH at the same time4)2CO3Aqueous solution or ammonia spirit and prepared
Mixed solution when generate or after prepared mixed solution is added with ammonium hydroxide or (NH4)2CO3Aqueous solution is adjusted
It arrives.
After being precipitated, in step iii) in, by the precipitation drying and roasting of separation, obtain recessed soil-titanium oxide-oxidation
Aluminium composite oxide carrier.The drying usually carries out at 50-120 DEG C, and drying time is usually 1-24 hours.Then, will
Dried precipitation roasting, this is realized advantageous by being roasted at a temperature of 450-600 DEG C, and roasting time is usually 2-6
Hour, so as to obtain recessed soil-titanium dioxide-aluminum oxide composite oxide carrier.Advantageously, by step ii) in gained be deposited in
It is aged, filters and washs at room temperature in its mother liquor, then re-dry and roasting.Roast the recessed soil-titanium oxide-oxygen obtained later
The specific surface area for changing aluminium composite oxide carrier is 80-180m2/ g, most probable pore size 9-19nm, and Kong Rongwei 0.4-
1.3ml/g。
In the manufacturing method of the selective hydrogenation catalyst of the present invention, step iv) specifically further include following steps：
I) at least hold recessed soil-titanium dioxide-aluminum oxide composite oxide carrier dipping with the composite oxide carrier hole etc.
The promoter metal compound solution of amount, the promoter metal is one or more in rare earth metal, and the carrier through dipping is done
Dry and roasting, is made catalyst semi-finished product, and based on the total weight of the catalyst semi-finished product, the content of promoter metal is 0-3 weights
% is measured, the preferably catalyst semi-finished product contain the cerium of 0-1 weight % as promoter metal；
II) by step I) in prepare catalyst semi-finished product palladium source compound solution dipping, then use hydrazine hydrate
(N2H4.H2O it) restores, washing, palladium supported catalyst is made in dry later and roasting, and the palladium metal content of the catalyst is
0.25-0.35 weight %, promoter metal content are 0-3 weight %；
III) optionally, by step II) gained palladium supported catalyst temperature be 100-150 DEG C, Hydrogen Vapor Pressure 2.0-
3.0MPa and hydrogen flowing quantity preferably restore 6-8h to be restored under conditions of 2-15ml/min.g.
Above-mentioned steps I) in roasting carried out at a temperature of 500-600 DEG C, preferably carry out 3-6 hours and/or step
Ii the roasting in) carries out at a temperature of 450-600 DEG C, preferably carries out 3-8 hours.
Above-mentioned steps II) in palladium source compound be one or more in being selected from the group：Palladium bichloride, palladium nitrate, sulfuric acid
Palladium, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, tetranitro palladium acid sodium, H2PdCl4With the acylate of palladium.
In order to carry out step I) in dipping, recessed native titanium dioxide-aluminum oxide composite oxide carrier is usually immersed into auxiliary agent
A period of time in metal compound solution, such as 5-20 minutes.The process advantageously carries out under stiring, in favor of carrier
It is sufficiently impregnated.After immersion, leaching removes extra maceration extract, by the carrier drying through dipping of gained, this usually in
A period of time is kept to realize, such as generally remain 8-12 hours to realize at a temperature of 100-150 DEG C.It then, will be through drying
Composite oxide carrier roasting, promoter metal compound is transformed into the oxide of promoter metal, this is usually in 500-600
At a temperature of kept for a period of time realize, such as generally remain 3-6 hours to realize.After roasting, catalyst half is obtained
Finished product.It is as described above catalyst semi-finished product are made after, carry out step II as described above), that is, by step I) in prepare urge
Palladium supported catalyst, the palladium of the catalyst is made in the solution dipping of agent semi-finished product palladium source compound, then dry and roasting
Tenor is 0.25-0.35 weight %, and promoter metal content is 0-3 weight %.In step II) in the palladium source compound that uses
Solution in, it can be water, methanol, ethyl alcohol or its mixture, it is preferable to use water conduct to be used to form the solvent that the solution uses
Solvent.As above-mentioned steps II) in the palladium source compound that uses, any palladium chemical combination for being suitable for preparing palladium catalyst can be used
Object, such as palladium bichloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, tetranitro palladium acid sodium, H2PdCl4, palladium has
Machine hydrochlorate (such as oxalic acid palladium) or its mixture.These palladium source compounds preferably with a concentration of 0.15-0.75g/ml, more preferably
The solution (preferred aqueous solutions) of 0.2-0.7g/ml uses.The dosage of palladium source compound solution answers immersion step I) in prepare urge
Agent semi-finished product, preferably its dosage use the solution of 0.5-3ml palladium source compounds for every gram of catalyst semi-finished product.Step I) in make
Standby catalyst semi-finished product are usually impregnated 0.5-2 hours with the solution of palladium source compound.
In above-mentioned steps II) in, after dipping, product is dry at 100-150 DEG C, this is usually carried out 4-8 hours.So
Afterwards, dried product is roasted at 450-600 DEG C, this is usually carried out 3-8 hours, and palladium supported catalyst is made.
In step II) after, by step II) in obtain palladium supported catalyst activated with hydrogen reducing.Alternatively, it walks
Rapid II) in obtain palladium supported catalyst can also be re-activated when being hydrogenated for drippolene.That is, preparing this hair
In the method for bright catalyst, step III) the step of being not required to carry out.
If carry out step III), step III) in palladium supported catalyst activation usually by its temperature be 100-
150 DEG C, Hydrogen Vapor Pressure be 2.0-3.0MPa and hydrogen flowing quantity be it is also original under conditions of 2-15ml/min.g catalyst carry out, it is excellent
Choosing reduction 6-8h.
The present invention also provides a kind of sides for carrying out selection plus hydrogen to drippolene using the selective hydrogenation catalyst
Method is included in the presence of the catalyst and the drippolene is carried out selecting to add hydrogen.
In a preferred embodiment of the present invention, the method further includes：Before the catalyst is used, in temperature
Spend for 100-150 DEG C, Hydrogen Vapor Pressure be 2.0-3.0MPa and hydrogen flowing quantity be 2-15ml/min.g under conditions of reduction described in urge
Agent.
In a preferred embodiment of the present invention, it is described select plus hydrogen temperature be 50-60 DEG C, pressure 2.6-
3.0MPa, hydrogen to oil volume ratio 50:1-80：1 and liquid hourly space velocity (LHSV) be 8-12h-1。
The preferred drippolene C of drippolene5-C9Fraction, especially C8And C9Double distilled.
In the selection method of hydrotreating of the present invention, the drippolene is that diene value is 20-40g iodine/100g oil and bromine valency
Feedstock oil for 40-70g bromines/100g oil.
The catalyst of the present invention is particularly suitable for drippolene C5-C9Fraction, especially C8And C9The selection of heavy distillat adds hydrogen.
For the selection plus hydrogen, optionally catalyst of the present invention is activated with hydrogen reducing first.If if carrying out, which leads to
It crosses catalyst of the present invention temperature is 100-150 DEG C, Hydrogen Vapor Pressure 2.0-3.0MPa and hydrogen flowing quantity are 2-15ml/min.g
Reduction carries out for a period of time under conditions of catalyst, preferably restores 6-8 hours.If it should be understood that in catalyst system
It, then, must in the method to drippolene progress selective hydrogenation of the present invention not by catalyst reduction activity during standby
It must carry out reduction activation.Then, temperature be 50-60 DEG C, pressure 2.6-3.0MPa, hydrogen to oil volume ratio 50:1-80：1 He
Liquid hourly space velocity (LHSV) is 8-12h-1Under conditions of hydrogenated pyrolysis gasoline.
Beneficial effects of the present invention：
The catalyst of the present invention is that rare earth compound is added in preparation process as auxiliary agent, impregnated by multistep and
It is obtained after high-temperature roasting.Compared with the prior art, it has the advantages that following prominent and effect：
1. the low temperature hydrogenation activity height that the catalyst of the present invention has, high selectivity.
The advantages that 2. the catalyst appearance glue and anticol performance of the present invention are good, hydrogenation activity is stablized, and service life is long.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the scope of the present invention is not limited to following embodiment.
Catalyst Preparation Example
Embodiment 1
Step 1
(1) using TiCl4The TiCl of 0.25mol/L is prepared with deionized water4Aqueous solution；
(2) using Al (NO3)3·9H2O crystal and the aluminum nitrate aqueous solution for removing to prepare 1.55mol/L from water；
(3) the recessed native aqueous solution of 10g/L is prepared from water using recessed soil and going；
(4) according to based on aluminum nitrate with Al2O3The weight TiCl of meter4With TiO2The content of meter is 20 weight % and recessed soil
Content is the amount of 1 weight %, and solution A, B and C are mixed, and obtains the mixed solution containing recessed soil, Ti and Al；
(5) using co-precipitation method, in 40 DEG C of water bath with thermostatic control, it is added dropwise 0.5mol/L's simultaneously under magnetic stirring
(NH4)2CO3Aqueous solution and the prepared mixed solution containing recessed soil, Ti and Al, the wherein rate of addition of mixed solution for 60 drops/
Minute, (NH4)2CO3The rate of addition of aqueous solution is 30 drops/minute；After being added dropwise to complete reaction is adjusted with the ammonium hydroxide of 0.5mol/L
The acid-base value of mixture forms precipitation to pH=8；
(6) being deposited in its mother liquor for gained is aged 12h at room temperature, filtered, is washed with deionized to no Cl—,
It is then placed in baking oven 12 hours dry at 100 DEG C, in 500 DEG C of roasting temperatures 4 hours, obtains recessed soil-titanium dioxide-oxygen
Change aluminium composite oxide carrier.In the carrier, the weight based on aluminium oxide, the content of recessed soil is 1 weight %, TiO2Content
For 20 weight %；And the specific surface area of the carrier is 128m2/ g, most probable pore size 18nm, Kong Rongwei 0.52ml/g.
Step 2
Recessed soil-titania-alumina the composite oxide carrier prepared in 97g steps 1 is taken, is added in thereto containing nitric acid
Cerium 0.2mol/L aqueous solutions 90ml is stirred 15 minutes, leaching removes extra maceration extract, then dry at 120 DEG C as maceration extract
Dry 10h roasts 4h at 550 DEG C, the catalyst semi-finished product containing cerium is made.
Step 3
The catalyst semi-finished product prepared in 100g steps 2 are immersed to the palladium chloride aqueous solution of a concentration of 0.509g/ml of 85ml
In, it takes out, drains after 1 hour, it is 6 hours dry at 120 DEG C, it is then roasted 4 hours at 480 DEG C, palladium-based catalyst is made
1。
The palladium content of palladium-based catalyst 1 is 0.3 weight %, and cerium content is 0.3 weight %, crushing strength 21N/mm；At this
In the carrier of catalyst, weight of the content based on aluminium oxide of recessed soil is 1 weight %, TiO2Weight of the content based on aluminium oxide
For 20 weight %.
Embodiment 2
The step 1-3 of embodiment 1 is repeated, unlike：In the sub-step (4) of step 1, according to based on aluminum nitrate with
Al2O3The weight TiCl of meter4With TiO2The content of meter is 20 weight %, and the amount that the content of recessed soil is 3 weight %, by solution
A, B and C mixing obtains the mixed solution containing recessed soil, Ti and Al.
As a result, in the recessed soil-titania-alumina composite oxide carrier obtained in step 1, the weight based on aluminium oxide
Amount, the content of recessed soil is 3 weight %, TiO2Content be 20 weight %；And the specific surface area of the carrier is 122m2/ g, most probable
Aperture is 17nm, Kong Rongwei 0.50ml/g.
As a result, obtain palladium-based catalyst 2 through step 3.The palladium content of palladium-based catalyst 2 be 0.3 weight %, cerium content 0.3
Weight %, crushing strength 21N/mm；In the carrier of the catalyst, weight of the content based on aluminium oxide of recessed soil is 3 weights
Measure %, TiO2Weight of the content based on aluminium oxide be 20 weight %.
Embodiment 3
The step 1-3 of embodiment 1 is repeated, unlike：The maceration extract of dipping complex carrier used in step 2 is changed into work
The lanthanum nitrate aqueous solution of the 0.2mol/L of 90ml.
As a result, finally obtain palladium-based catalyst 3.The palladium content of palladium-based catalyst 3 is 0.3 weight %, and lanthanum content is 0.3 weight
Measure %, crushing strength 21N/mm；In the carrier of the catalyst, weight of the content based on aluminium oxide of recessed soil is 1 weight %,
TiO2Weight of the content based on aluminium oxide be 20 weight %；And the specific surface area of the carrier is 128m2/ g, most probable pore size are
18nm, Kong Rongwei 0.52ml/g.
Embodiment 4
The step 1-3 of embodiment 1 is repeated, unlike：The maceration extract of dipping complex carrier used in step 2 is changed into work
The praseodymium nitrate aqueous solution of the 0.2mol/L of 90ml.
As a result, obtaining the catalyst semi-finished product containing praseodymium in step 2, and palladium-based catalyst 4 is obtained through step 3.Palladium base
The palladium content of catalyst 4 is 0.3 weight %, and praseodymium content is 0.3 weight %, crushing strength 21N/mm；In the carrier of the catalyst
In, weight of the content based on aluminium oxide of recessed soil is 1 weight %, TiO2Weight of the content based on aluminium oxide be 20 weight %；And
And the specific surface area of the carrier is 128m2/ g, most probable pore size 18nm, Kong Rongwei 0.52ml/g.
Embodiment 5
The step 1-3 of embodiment 1 is repeated, unlike：The maceration extract of dipping complex carrier used in step 2 is changed into work
The mixed aqueous solution 90ml of the 0.13mol/L containing cerous nitrate.
As a result, obtaining the catalyst semi-finished product containing cerium in step 2, and palladium-based catalyst 5 is obtained through step 3.Palladium base
The palladium content of catalyst 5 is 0.3 weight %, and cerium content is 0.2 weight %, crushing strength 21N/mm；In the carrier of the catalyst
In, weight of the content based on aluminium oxide of recessed soil is 1 weight %, TiO2Weight of the content based on aluminium oxide be 20 weight %；And
And the specific surface area of the carrier is 128m2/ g, most probable pore size 18nm, Kong Rongwei 0.52ml/g.
Comparative example 1
The step 1-3 of embodiment 1 is repeated, unlike：The maceration extract of dipping complex carrier used in step 2 is changed into work
90ml deionized waters.
As a result, the catalyst semi-finished product obtained in step 2 are free of rare earth metal, and comparison catalysis is obtained through step 3
Agent 1.The palladium content of comparative catalyst 1 is 0.3 weight %, crushing strength 21N/mm；In the carrier of the catalyst, recessed soil
Weight of the content based on aluminium oxide is 1 weight %, TiO2Weight of the content based on aluminium oxide be 20 weight %；And the carrier
Specific surface area is 128m2/ g, most probable pore size 18nm, Kong Rongwei 0.52ml/g.
Comparative example 2
The step 1-3 of embodiment 1 is repeated, unlike：Omit the sub-step (3) of step 1, as a result, obtain two in step 1
Titanium dioxide-aluminum oxide carrier；The specific surface area of the carrier is 120m2/ g, most probable pore size 16nm, Kong Rongwei 0.49ml/g.
As a result, the catalyst semi-finished product containing cerium are obtained through step 2.
As a result, obtain comparative catalyst 2 through step 3.The palladium content of comparative catalyst 2 be 0.3 weight %, cerium content 0.3
Weight %, crushing strength 21N/mm.
Comparative example 3
The step 1-3 of embodiment 1 is repeated, unlike：Omit the sub-step (1), (3) and (4) of step 1, as a result, in step
Rapid 1 obtains alumina support；The specific surface area of the carrier is 122m2/ g, most probable pore size 17nm, Kong Rongwei 0.50ml/g.
As a result, the catalyst semi-finished product containing cerium are obtained through step 2.
As a result, obtain comparative catalyst 3 through step 3.The palladium content of comparative catalyst 3 be 0.3 weight %, cerium content 0.3
Weight %, crushing strength 21N/mm.
The content of the respective rare earth metal auxiliary agents of palladium-based catalyst 1-5 and comparative catalyst 1-3 is shown in Table 1.
Table 1
Embodiment 9
This example demonstrates that the catalyst obtained by embodiment 1-5 and comparative example 1-3 is in drippolene C8Fraction selective hydrogenation
In application.
Evaluating catalyst experiment adds in 100ml small fixeds to be carried out on hydrogen evaluating apparatus, the reactor of the evaluating apparatus
It is reaction tube, reaction tube length 1.2m, internal diameter 26mm, loaded catalyst 100ml.
Catalyst 1-5 made from Example 1-5 and comparative example 1-3 and each 100ml of comparative catalyst 1-3 are loaded into respectively
It is 2.8MPa in Hydrogen Vapor Pressure, temperature is 110 DEG C and hydrogen flowing quantity is that 4ml/min.g is urged in the reaction tube for adding hydrogen evaluating apparatus
It is restored 8 hours under conditions of agent.Then cool down, be later 2.8Mpa in Hydrogen Vapor Pressure, reaction temperature is 50 DEG C, hydrogen oil volume
Than being 80：1, total liquid hourly space velocity (LHSV) is 12h-1Under conditions of be passed through diene value be 20.27g iodine/100g oil, bromine valency be 40.36g bromines/
100g oil, gum level are 232mg/100ml oil, nitrogen content is 3.4mg/100ml oil, oxide content 2.19g/100ml
Oil, the drippolene C that sulfur content is 110ppm and arsenic content is 180ppb8Fraction adds hydrogen to the results are shown in Table 2.
Table 2
Note：* bromine valency is to weigh an index of unsaturated hydrocarbons content in drippolene.Bromine valency is higher, then illustrates in sample
Unsaturated hydrocarbons content is higher, i.e., degree of unsaturation is higher.
In drippolene drippolene can be seriously affected containing dienes, the presence of diene such as styrene and conjugated dienes
Stability, so diene value is bigger, drippolene gets over unstability.
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 additives（Catalyst 1,3 and 4）, different rare-earth additive content（Catalyst 1 and 5）, different recessed native contents（Catalyst 1
With 2）The catalytic effect of catalyst is influenced little.
When not containing rare-earth additive and recessed soil in catalyst（Comparative catalyst 1,2 and 3）When, the catalytic performance of catalyst is fast
Speed declines.
Embodiment 10
Palladium-based catalyst 1100ml made from Example 1 is packed into 100ml small fixeds and adds in hydrogen evaluating apparatus,
The reactor of the device is reaction tube, reaction tube length 1.2m, internal diameter 26mm.The process conditions such as reaction temperature, pressure are by microcomputer
It automatically controls.It is 2.8MPa in Hydrogen Vapor Pressure, temperature is 110 DEG C and hydrogen flowing quantity is 4ml/min.g after the completion of Catalyst packing
It is restored 8 hours under conditions of catalyst.Then cool down, be later 2.8MPa in Hydrogen Vapor Pressure, reaction temperature is 50 DEG C, hydrogen oil body
Product is than being 80：1, charging liquid hourly space velocity (LHSV) is 8h-1Under conditions of to be passed through diene value be 20.27g iodine/100g oil, bromine valency 40.36g
Bromine/100g oil, gum level are 232mg/100ml oil, nitrogen content is 3.4mg/100ml oil, oxide content 2.19g/
100ml oil, the drippolene C that sulfur content is 110ppm and arsenic content is 180ppb8Fraction, fresh feed liquid hourly space velocity (LHSV) are 2.0
When-1, 1000 hours reaction time added hydrogen result such as the following table 3.
Table 3
According to 3 column datas of table it is found that palladium-based catalyst 1 has good stability.
Claims (15)
1. a kind of selective hydrogenation catalyst, including：
A) using recessed soil-titanium dioxide-aluminum oxide composite oxides as carrier, the content of the carrier concave soil is alumina weight
0.1-3 weight %, the content of titanium oxide is the 5-20 weight % of alumina weight in the carrier；
B) activity component metal palladium, the content of the Metal Palladium are the 0.25-0.35 weight % of the total catalyst weight；
C) at least one selected from the accelerating agent based on rare earth metal, the content of the accelerating agent is the 0- of the total catalyst weight
3 weight %.
2. catalyst according to claim 1, which is characterized in that recessed soil-titanium dioxide-aluminum oxide composite oxide carrier
Specific surface area is 80-180m2/ g, most probable pore size 9-19nm, Kong Rongwei 0.4-1.3ml/g, and crushing strength is more than
18N/mm。
3. catalyst according to claim 1 or 2, which is characterized in that recessed soil-titanium oxide-oxygen in the catalyst
Change in aluminium composite oxide carrier, the content of recessed soil is the weight 0.5-3 weight % of aluminium oxide, and the content of titanium oxide is aluminium oxide
Weight 10-20 weight %.
4. catalyst according to claim 1 or 2, which is characterized in that the content of the accelerating agent is total for the catalyst
The 0-1 weight % of weight.
5. catalyst according to claim 1 or 2, which is characterized in that the rare earth metal in lanthanum, cerium and praseodymium extremely
Few one kind.
6. catalyst according to claim 1 or 2, which is characterized in that nitrate of the accelerating agent selected from rare earth metal,
At least one of sulfate, chloride, acylate and acetylacetonate.
7. catalyst according to claim 6, which is characterized in that the accelerating agent is selected from lanthanum nitrate, cerous nitrate and nitric acid
At least one of praseodymium.
8. a kind of manufacturing method of selective hydrogenation catalyst according to any one of claim 1-7, includes the following steps：
I) recessed soil paste liquid is mixed 10-24 hours to obtain in recessed soil and hydrochloric acid solution, upper strata suspension is taken after standing, on described
Layer suspension is filtered, the recessed soil dried to the solid matter after filtering, ground after purification；
Ii recessed soil, titanium-containing compound and aluminum contained compound) are mixed to get mixed solution, using co-precipitation method, described
(NH is added in mixed solution4)2CO3Aqueous solution or ammonia spirit are mixed to form precipitation；In the mixed solution it is recessed soil,
The content of titanium compound and aluminium compound should cause：Weight based on aluminium compound in terms of aluminium oxide, the content of recessed soil is 0.1-3
Weight %, and titanium compound is using the content that titanium dioxide is counted as 5-20 weight %；
Iii) gained precipitates in separating step (ii), by the precipitation drying and roasting of separation, obtains recessed soil-titanium dioxide-aluminum oxide
Composite oxide carrier；
Iv step iii) is carried on by the component b) and c)) obtained recessed soil-titanium dioxide-aluminum oxide composite oxide carrier
On, so as to obtain the catalyst.
9. according to the method described in claim 8, it is characterized in that, in step ii) in, the recessed soil, titanium-containing compound and
Solvent is added in aluminum contained compound and forms mixed solution, the solvent is selected from least one of water, methanol and ethyl alcohol.
10. method according to claim 8 or claim 9, which is characterized in that the titanium-containing compound is selected from acetate, the salt of titanium
Hydrochlorate and nitrate at least one or in tetraethyl titanate, four n-propyl of metatitanic acid and tetra-n-butyl titanate at least one
Kind；The aluminum contained compound is selected from least one of aluminum nitrate, aluminium chloride, aluminum sulfate and their hydrate.
11. a kind of selective hydrogenation catalyst of use according to any one of claim 1-7 selects drippolene
Add the method for hydrogen, be included in the presence of the catalyst and the drippolene is carried out selecting to add hydrogen.
12. according to the method for claim 11, which is characterized in that the method further includes：Use the catalyst it
Before, temperature is 100-150 DEG C, Hydrogen Vapor Pressure is 2.0-3.0MPa and hydrogen flowing quantity be 2-15ml/min.g under conditions of restore
The catalyst.
13. the method according to claim 11 or 12, which is characterized in that the temperature for selecting to add hydrogen is 50-60 DEG C, presses
Power is 2.6-3.0MPa, hydrogen to oil volume ratio 50:1-80：1 and liquid hourly space velocity (LHSV) be 8-12h-1。
14. the method according to claim 11 or 12, which is characterized in that the drippolene is drippolene C5-C9It evaporates
Point.
15. according to the method for claim 14, which is characterized in that the drippolene be diene value for 20-40g iodine/
100g oil and the feedstock oil that bromine valency is 40-70g bromines/100g oil.
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| CN108499559B (en) * | 2017-02-28 | 2021-02-05 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application thereof |
| CN108855090B (en) * | 2017-05-08 | 2021-02-05 | 中国石油化工股份有限公司 | Ethylene glycol hydrogenation catalyst and preparation method thereof |
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| GB1191471A (en) * | 1967-08-07 | 1970-05-13 | Union Oil Co | Integral Hydrocracking-Hydrotreating Process |
| CN102527367A (en) * | 2010-12-27 | 2012-07-04 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of cracked gasoline and preparation and application thereof |
| 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 |
| CN103100379A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Production method of titanium oxide-alumina composite |
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| CN102527367A (en) * | 2010-12-27 | 2012-07-04 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of cracked gasoline and preparation and application thereof |
| 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 |
| CN103100379A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Production method of titanium oxide-alumina composite |
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