CN102451685B - Selective hydrogenation catalyst and preparation method thereof - Google Patents
Selective hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102451685B CN102451685B CN201010514491.3A CN201010514491A CN102451685B CN 102451685 B CN102451685 B CN 102451685B CN 201010514491 A CN201010514491 A CN 201010514491A CN 102451685 B CN102451685 B CN 102451685B
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Abstract
The present invention discloses a selective hydrogenation catalyst and a preparation method thereof. According to the catalyst, macroporous alumina is adopted as a carrier, an active metal component is palladium, an additive component is Mo and/or Co, and the active metal component and the additive component are distributed on the carrier surface in an eggshell form. The macroporous alumina is prepared by a sodium aluminate and carbon dioxide precipitation method, wherein the single flow coprecipitation is performed under the conditions that the pH value of one part of the sodium aluminate is changed and the pH value of the other part of the sodium aluminate is maintained to the constant value, and a polymer surfactant is added. The resulting macroporous alumina by the method has large specific surface area and large pore volume, and the pore size distribution is centralized in the range of 10-20 nm so as to contribute to improvement of the hydrogenation activity and the selectivity of the catalyst. In addition, the interaction can be generated between the additive component and the active component palladium so as to contribute to the uniform distribution of the palladium particles, and enhance the interaction between the palladium and the carrier, such that the palladium loss is reduced, the palladium utilization rate is improved, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of selective hydrocatalyst and preparation method thereof, this catalyst is applicable to the medium-low distillate oil selective hydrogenation, is specially adapted to drippolene C
9the cut fraction section selective hydrogenation process.
Background technology
Take lighter hydrocarbons, naphtha, diesel oil or heavy oil as raw material, under steam exists, in the process of Pintsch process preparing ethylene, generate the above liquid by-product of carbon containing five hydro carbons, through fractionating out, to do be that the liquid of 205 ℃ is called drippolene.Cracking of ethylene C
9cut is to isolate C by drippolene through extracting
5cut, C
6～C
8residue cut after cut, account for 10%～20% of ethene total output.
Along with suddenly increasing of developing rapidly of petroleum chemical industry, particularly ethylene production capacity, cracking of ethylene C
9the quantity of cut also grows with each passing day.Be an important branch in field of hydrogenation and take the hydrogen addition technology that pyrolysis gasoline hydrogenation catalyst is core, occupy very important position in the post processing of preparing ethylene by steam cracking technology.How rationally to utilize this part resource, the exploitation downstream product more and more receives the concern of industry.
Cracking of ethylene C
9cut low pressure two-stage hydrogenation is produced the aromatic solvent oil tech, is under the process conditions that relax, and carries out selective hydrogenation and removing diolefin, styrene and derivative and monoolefine, and removes sulphur, nitrogen impurity, produces stable aromatic hydrocarbon solvent oil.
Current industrial pyrolysis gasoline hydrogenation catalyst mainly contains palladium system and nickel is two kinds of catalyst, but still take palladium series catalyst as main.The advantages such as it is low that palladium series catalyst has start-up temperature, and hydrogenation activity is high, and the material handling amount is large, and catalyst life is long.But due to the impact that is subject to the ethylene raw diversification, cut is laid particular stress in recent years, the hydrogenation load is bigger than normal, causes existing catalyst stability in industrial operation poor, and catalyst life is short.
CN 200410061031.4 discloses a kind of palladium-aluminium oxide catalyst and preparation method thereof, and it relates to a kind of Sq alkaline earth oxide that applies in advance, and through hard burned Al
2o
3for carrier, palladium-impregnated content is that 0.15wt%～0.24wt% makes catalyst.CN1435277A discloses a kind of for process for prepairng hydrogen peroxide by anthraquinone load type palladium-aluminium oxide catalyst and preparation method thereof, and it relates to a kind of Sq rare earth oxide that applies in advance, and through 900～1000 ℃ of baked Al of high temperature
2o
3for carrier, palladium-impregnated content is that 0.15wt%～0.25wt% makes catalyst.CN85100761A discloses a kind of fiber catalyst carrier for the pyrolysis gasoline cut fraction diolefin selective hydrogenation, and specific area is 20～200m
2/ g, η-Al of pore volume 0.1～0.3ml/g
2o
3porous fibrous carrier, this catalyst initial activity is high, but pore volume is too little, and when in the raw material of pyrolysis gasoline hydrogenation device, colloid etc. exceeds standard, the easy coking and blocking of pore volume on catalyst, affect the catalyst hydrogenation stability.
US 3,898, and 298 disclose a kind of precious metals pd catalyst, and it is to using Pd that content is 0.05wt%～0.2wt% as active component, and aluminium oxide is carrier, and this hydrogenation catalyst is only applicable to the C of alkynes content low (1.0wt% is following)
4the selective hydrogenation of cut.
CN101433841A discloses a kind of selective hydrocatalyst, take aluminium oxide as carrier, and the content of active component Pd is 0.2wt%～0.5wt%, auxiliary agent lanthanum and/or cerium 2.0wt%～8.0wt%, catalyst specific surface 70～150m
2/ g, pore volume 0.3～0.6ml/g, the crystal formation of carrier is the θ type or take the θ type as main θ, α mixing crystal formation.This catalyst is applicable to the full cut of drippolene, and for heavier cut, due to specific area and pore volume relatively low, affect the activity and selectivity of catalyst, and the catalyst rapid deactivation, the poor stability of catalyst, the cycle is short, has increased operating cost.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of selective hydrocatalyst and preparation method thereof.This catalyst has larger pore volume and specific area, and stronger anticol mass-energy power is arranged, and the activity and selectivity of catalyst is high, and good stability is specially adapted to drippolene C
9in the hydrogenation process of cut.
Selective hydrocatalyst of the present invention, take macroporous aluminium oxide as carrier, active metal component is palladium, adjuvant component is Mo and/or Co, and active metal component and adjuvant component are eggshell type at carrier surface and distribute, and shell thickness is 0.05～0.20mm, the weight of catalyst of take is benchmark, the content of active metal component Pd is 0.1%～0.5%, the content of auxiliary agent Mo and/or Co is 2.0%～10.0%, and macroporous aluminium oxide content is 60%～90%, and the content of adhesive is 5%～30%.
Selective hydrocatalyst character of the present invention is as follows: specific area is 150～280m
2/ g, pore volume is 0.7～1.0ml/g.
Described macroporous aluminium oxide has following character: specific area is 300～500m
2/ g, pore volume is 0.8～1.5ml/g, and the pore volume that bore dia is 10～20nm accounts for 50%～70% of total pore volume, and preferred property is as follows: specific area is 400～500m
2/ g, pore volume is 0.9～1.5ml/g, bore dia is that the shared pore volume of 10～20nm is total pore volume 55%～70%.
The character of above-mentioned macroporous aluminium oxide is the character of macropore aluminium hydroxide through 350～650 ℃ of roastings macroporous aluminium oxide of gained after 1～10 hour.
The preparation method of catalyst of the present invention is as follows: to adding adhesive, peptizing agent kneading in macropore aluminium hydroxide, roll agglomerating after, through moulding, drying and roasting, obtain alumina support, then supported active metal component and adjuvant component, drying and roasting, obtain selective hydrocatalyst again; Wherein, the preparation process of described macropore aluminium hydroxide, comprise the steps:
A, the first sodium aluminate solution is joined in plastic cans, ventilate simultaneously and pass into CO
2gas, control pH value to 11.0～13.0, and the neutralization reaction time is 1～2 hour;
B, then increase CO
2addition, add the second sodium aluminate solution in the material of step a gained, controlling the pH value constant is 8.0～11.0, adds 3%～5% the high molecular surfactant that accounts for step e gained aluminium hydroxide (in aluminium oxide) weight simultaneously, and the neutralization reaction time is 0.5～1.0 hour;
C, at the control temperature and pH value of step b, said mixture ventilates and to stablize 1～3 hour;
D, the solidliquid mixture of step c gained is filtered and washs;
The solids drying of e, steps d gained obtains macropore aluminium hydroxide.
In step a, the concentration of the first sodium aluminate solution is 15～60gAl
2o
3/ l, be preferably 20～40gAl
2o
3/ l.In step b, the concentration of the second sodium aluminate solution is 15～60gAl
2o
3/ l, be preferably 20～40gAl
2o
3/ l.Wherein, the first sodium aluminate solution and the second sodium aluminate solution can adopt identical concentration, also can adopt different concentration.
It is 20～40 ℃ that step a controls reaction temperature.
Described CO
2the concentration of gas is 10v%～60v%.
In the inventive method, the addition of the first sodium aluminate solution accounts for the gross weight of the first sodium aluminate solution and the second sodium aluminate solution and counts 30%～50% with aluminium oxide.
Step b, described high molecular surfactant is one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, AEO, fatty alkanol amide and polyacrylamide, the molecular weight of above-mentioned high molecular surfactant is 1.8～2.3 ten thousand.
Increase CO described in step b
2addition can be passed through CO
2concentration and/or flow are regulated.
The described washing of steps d is to be washed till neutrality by the deionized water of 40～90 ℃; The described drying condition of step e is 110～130 ℃ of dryings 4～10 hours.
In aluminium hydroxide preparation process involved in the present invention, the first sodium aluminate solution neutralization reaction pH value controls to 11.0～13.0, is preferably 11.5～12.0, the second sodium aluminate solution and CO
2pH value in reaction is general constant is 8.0～11.0, is preferably 10.0～11.0.It is lower by 0.3～4.0 than the pH value of step a control reaction end that step b controls constant pH value, is preferably 1.0～2.0.
In the preparation process of catalyst carrier of the present invention, described adhesive can adopt conventional adhesive, is preferably little porous aluminum oxide.Described peptizing agent can adopt organic acid and/or inorganic acid, and as one or more in nitric acid, hydrochloric acid, formic acid, acetic acid, citric acid, the addition of peptizing agent accounts for 0.5%～10.0% of catalyst weight.In the carrier forming process, can also add as required extrusion aid, such as the sesbania powder.
Described carrier moulding, can be made into various shapes depending on different demands, and such as spherical, tablet, annular, hollow cylinder or bar shaped etc. is better bar shaped (clover, bunge bedstraw herb, cylindrical bars etc.), is preferably the cylindrical bars of 3～8 millimeters of diameters.Drying condition after the carrier moulding is as follows: 80～120 ℃ of dryings 2～15 hours, roasting condition was as follows: 900～1200 ℃ of roastings 4～8 hours.
In the present invention, the load of active metal component and adjuvant component adopts routine techniques, such as the infusion process preparation, preferably adopt the method that sprays, active metal component and adjuvant component adopt the method for dipping respectively to load on alumina support, and be eggshell and be distributed on carrier surface, detailed process is as follows: alumina support sprays the maceration extract containing palladium, then at 100～130 ℃ of dry 6-14 hour, 450～550 ℃ of roastings 5～10 hours, obtain the palladium-containing catalyst intermediate, adopt again the method sprayed will spray containing the maceration extract of Mo and/or W on the palladium-containing catalyst intermediate, then through 100～130 ℃ of dryings 6～14 hours, 500～600 ℃ of lower roastings 5～10 hours, obtain selective hydrocatalyst.
The present invention can adopt the method preparation of conventional eggshell type containing the palladium maceration extract containing the maceration extract of palladium, specific as follows: the palladium content that takes aequum is no less than the palladium bichloride powder of 59wt%, add water, add again hydrochloric acid, dilution after dissolving, regulate the pH value according to required shell thickness, pH value scope is 3.0～6.0.
The present invention can adopt the conventional method preparation containing the maceration extract of Mo and/or W, and the molybdenum salt and/or the tungsten salt that are about to solubility are added to the water dissolving and obtain.
Selective hydrocatalyst of the present invention is applicable to medium-low distillate oil and selects hydrogenation, is specially adapted to drippolene C
9the cut fraction section selective hydrogenation process.Catalyst of the present invention is applicable to fixed bed reactors usually, and the operating condition of employing is as follows: reaction temperature is 70～170 ℃, reaction pressure 1.0～4.0MPa, hydrogen to oil volume ratio 300～500, volume space velocity 1.0～3.0h during liquid
-1.
The inventive method macropore aluminium hydroxide used is to adopt a part of sodium aluminate change pH values, prepared by the coprecipitated method of the permanent pH value single current of a part of sodium aluminate, and not only process is simple, easy to control, adopts CO simultaneously
2stir with wind, make the full and uniform mixing of reactant.In the plastic process, small part sodium aluminate change pH values, form the hole of inhomogeneous dispersion, strengthens afterwards CO
2amount, add fast another part sodium aluminate under the condition of constant lower pH value, the pH value of follow-up plastic process is lower, make the previous small structure generated peptization again, and follow-up colloid is generated rapidly equably, and add surfactant simultaneously, not only played the effect of expanding agent, and surfactant is embedded in reaction structure, with surface hydroxyl, interact, increased the specific area of carrier and the dispersiveness of material, improved pore size distribution, made pore distribution concentration in the 10-20nm scope.In addition, neutralization reaction has increased ageing process after finishing, and has so both guaranteed that reactant reaction is complete, also is conducive to the growth of particle species, thereby makes alumina support have larger specific area and pore volume, and the aperture of pore distribution concentration is larger simultaneously.
Alumina support that the present invention adopts has larger specific area and pore volume, the aperture of pore distribution concentration is larger, not only for reactant, enough passages are provided, be conducive to the turnover of reactant and product, effectively avoided the polymerization of unsaturated hydrocarbons, block duct, larger space and specific area bearing metal also is provided in addition, make hydrogenation metal there is higher dispersiveness, make catalyst of the present invention not only there is suitable activity, have more high hydrogenation selectivity.Due to active component palladium and C
9complex reaction easily occurs in the unsaturated hydrocarbons in cut, can make palladium run off gradually, thereby cause catalysqt deactivation.The promoter metal of adding in the present invention can and active component palladium between produce to interact, and be conducive to being uniformly distributed of palladium particle, also can strengthen the interaction between palladium and carrier, thereby reduce the loss of palladium simultaneously, improve the utilization rate of palladium, extending catalyst service life.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described.In the present invention, wt% is mass fraction, and v% is volume fraction.
In the present invention, pore structure and specific area are to adopt the low temperature liquid nitrogen determination of adsorption method.
Embodiment 1
It is 200gAl that solid sodium aluminate is mixed with to concentration
2o
3the dense sodium aluminate solution of/l, then to be diluted to concentration be 25gAl
2o
3/ L and 35gAl
2o
3/ L sodium aluminate working solution, the steel plastic cans of getting a 30L, first add 5L to contain 25gAl
2o
3/ L sodium aluminate working solution, ventilate simultaneously and pass into the CO that concentration is 45v%
2gas, 25 ℃ of reaction temperatures, the reaction time is 1 hour, the pH value, by 11.5 o'clock, is adjusted rapidly CO
2flow, add 8.3L to contain 35gAl
2o
3the sodium aluminate working solution of/L adds the polyethylene glycol that the 17g molecular weight is 20,000 simultaneously, makes the pH of system remain on 10.0 left and right, 25 ℃ of reaction temperatures, and the reaction time is 1 hour, after question response is complete, stops passing into CO
2, then ventilating and stablize 60 minutes, slurries filter and use 60 ℃ of deionized waters to be washed till neutrality, then, 120 ℃ of dryings 8 hours, obtain macropore aluminium hydroxide Y-1.Through 550 ℃ of roastings 5 hours, obtain macroporous aluminium oxide A-1, its character is in Table 1.
Embodiment 2
It is 200gAl that solid sodium aluminate is mixed with to concentration
2o
3the dense sodium aluminate solution of/l, then to be diluted to concentration be 25gAl
2o
3/ L sodium aluminate working solution, the steel plastic cans of getting a 30L, first add 5L to contain 25gAl
2o
3/ L sodium aluminate working solution, ventilate simultaneously and pass into the CO that concentration is 40v%
2gas, 25 ℃ of reaction temperatures, the reaction time is 1.2 hours, the pH value, by 12.0 o'clock, is adjusted rapidly CO
2flow, add 11L to contain 25gAl
2o
3the sodium aluminate working solution of/L adds the polyethylene glycol that the 21g molecular weight is 20,000 simultaneously, makes the pH of system remain on 10.0 left and right, 25 ℃ of reaction temperatures, and the reaction time is 0.8 hour, after question response is complete, stops passing into CO
2, then ventilating and stablize 60 minutes, slurries filter and use 60 ℃ of deionized waters to be washed till neutrality.120 ℃ of dryings 8 hours, obtain macropore aluminium hydroxide Y-2.Through 550 ℃ of roastings 5 hours, obtain macroporous aluminium oxide A-2, its character is in Table 1.
Embodiment 3
Carrier A involved in the present invention, catalyst intermediate TA and catalyst catA.Get 85g macropore aluminium hydroxide Y-1,66g aperture SB aluminium oxide and the rare nitric acid kneading of 4g, roll, but make the paste of extrusion, extruded moulding, 110 ℃ of dryings 2 hours, 1000 ℃ of roastings 4 hours, make carrier A.
Take the palladium bichloride powder that 0.5g palladium content is no less than 59wt%, add water, then add hydrochloric acid, be diluted to 80ml after dissolving, regulate pH value to 3.5; Take the 100g carrier A, the palladium chloride solution prepared is sprayed on carrier A, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours, make catalyst intermediate TA.
Take ammonium heptamolybdate 3.7g, be configured to the 80ml aqueous solution, spray above-mentioned catalyst intermediate TA upper, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours.
Embodiment 4
Carrier B involved in the present invention, catalyst intermediate TB and catalyst catB.Get 100g macropore aluminium hydroxide Y-2,60g aperture SB aluminium oxide and the rare nitric acid kneading of 2.7g, roll, but make the paste of extrusion, extruded moulding, 110 ℃ of dryings 2 hours, 1000 ℃ of roastings 4 hours, make carrier B.
Take the palladium bichloride powder that 0.8g palladium content is no less than 59wt%, add water, then add hydrochloric acid, be diluted to 80ml after dissolving, regulate pH value to 4.0; Take the 100g carrier B, the palladium chloride solution prepared is sprayed on carrier B, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours, make catalyst intermediate TB.
Take ammonium metatungstate 3.9g, be configured to the 80ml aqueous solution, spray above-mentioned catalyst intermediate TB upper, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours, make catalyst finished product catB.
Comparative example 1
It is 200gAl that the 700g solid sodium aluminate is mixed with to concentration
2o
3the dense sodium aluminate solution of/l, then to be diluted to concentration be 35gAl
2o
3/ L sodium aluminate working solution (a), the steel plastic cans of getting a 30L, open the container valve that has (a), ventilates simultaneously and pass into the CO that concentration is 45v%
2gas, the flow of setting (a) makes the reaction time at 1 hour, and adjusts rapidly CO
2flow, make the pH of system remain on 10.0 left and right, 25 ℃ of reaction temperatures, after (a) reacted, stop passing into CO
2, slurries filter and use 60 ℃ of deionized waters to be washed till neutrality.120 ℃ of dryings 8 hours, obtain reference aluminium oxide DY-1.Through 550 ℃ of roastings 5 hours, obtain aluminium oxide DA-1, its character is in Table 1.
Comparative example 2
The preparation of reference carrier DA, reference catalyst intermediate DTA and reference catalyst DcatA.
Get 85g reference aluminium oxide DY-1,66g aperture SB aluminium oxide and the rare nitric acid kneading of 4g, roll, but make the paste of extrusion, extruded moulding.110 ℃ of dryings 2 hours, 1000 ℃ of roastings 4 hours, make carrier DA.
Take the palladium bichloride powder that 0.5g palladium content is no less than 59wt%, add water, then add hydrochloric acid, be diluted to 80ml after dissolving, according to required shell thickness, regulate the pH value; Take 100g carrier DA, the palladium chloride solution prepared is sprayed to carrier DA upper, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours, make catalyst intermediate DTA.
Take ammonium molybdate 3.7g, be configured to the 80ml aqueous solution, spray catalyst intermediate DTA upper, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours, make catalyst finished product DcatA.
The physico-chemical property of table 1 macroporous aluminium oxide
| The aluminium oxide numbering | A-1 | A-2 | DA-1 |
| Specific area/m 2.g -1 | 440 | 480 | 245 |
| Pore volume/ml.g -1 | 1.20 | 1.40 | 0.60 |
| Pore size distribution, % | |||
| ＜6nm | 7.3 | 6.0 | 11.4 |
| 6～10nm | 12.2 | 10.1 | 32.7 |
| 10～20nm | 62.1 | 65.2 | 39.5 |
| 20～30nm | 12.7 | 13.0 | 11.3 |
| ＞30nm | 5.2 | 5.7 | 5.1 |
Table 2 carrier and catalyst physico-chemical property
| The catalyst numbering | catA | catB | DcatA |
| Pd，wt％ | 0.29 | 0.45 | 0.30 |
| Mo，wt％ | 2.10 | - | 2.20 |
| W，wt％ | - | 3.7 | - |
| Macroporous aluminium oxide, wt% | 74 | 86 | 74 |
| Adhesive, wt% | Surplus | Surplus | Surplus |
| Shell thickness, mm | 0.15 | 0.16 | 0.16 |
| Specific area/m 2.g -1 | 291 | 276 | 175 |
| Pore volume/ml.g -1 | 0.84 | 0.95 | 0.39 |
As can be seen from Table 2, comparative example carrier and catalyst pore volume, specific surface and aperture are all lower, can affect undoubtedly metal and obtain decentralization, can not, for reactant provides enough passages, affect the turnover of reactant and product in addition.The invention described above catalyst and comparative example catalyst are carried out to active evaluation test.By the activity that generates oily diene content sign catalyst.
Embodiment 5
Raw material cracking of ethylene C for test
9cut, test is deoxidation with hydrogen and crosses through silica gel-molecular sieve dehydration purified treatment, the electrolysis hydrogen of hydrogen purity>99v%, employing catalyst catA.The evaluating catalyst test is carried out on small hydrogenation device.Volume space velocity 1.0h when 80 ℃ of reaction temperatures, hydrogen dividing potential drop 3.0MPa, liquid
-1with hydrogen to oil volume ratio 300: 1, products obtained therefrom character was in Table 3.
Embodiment 6
The evaluate catalysts process is with embodiment 5, and evaluate catalysts is catB, and products obtained therefrom character is in Table 3.
Comparative example 3
The evaluate catalysts process is with embodiment 5, and evaluate catalysts is DcatA, and products obtained therefrom character is in Table 3.
Table 3 catalyst initial activity is estimated
| Character | Raw material | Embodiment 5 | Embodiment 6 | Comparative example 3 |
| Diene/g. (100g) -1 | 8.2 | 1.1 | 1.2 | 2.3 |
| Existent gum/mg. (100ml) -1 | 80 | 59 | 60 | 78 |
| Sulphur/μ gg -1 | 181.5 | 178.6 | 78.9 | 179.1 |
| Nitrogen/μ gg -1 | 30.2 | 28.5 | 28.6 | 28.7 |
| Aromatic hydrocarbons, v% | 93.68 | 93.51 | 93.50 | 93.49 |
| Iodine number/gI. (100ml) -1 | 97.1 | 45.3 | 46.9 | 70.7 |
| De-diene rate, wt% | - | 86.58 | 85.37 | 71.95 |
| Liquid is received, wt% | - | 100.11 | 100.08 | 99.74 |
From table 3, adopt the catA catalyst, the diene content of hydrogenated products significantly descends, and de-diene rate reaches 86.58%, and iodine number is reduced to 45.3gI/100ml by 97.1gI/100ml, and existent gum is down to 59mg/100ml by 80mg/100ml; Adopt the product property of catB catalyst basic identical with the product property that adopts catA, and employing DcatA catalyst, de-diene rate 71.95%, iodine number is reduced to 70.7gI/100m by 97.10gI/100ml, existent gum is down to 78mg/100ml by 80mg/100ml, has absolutely proved that selective hydrocatalyst of the present invention has stronger hydrogenation activity and selective.
Claims (14)
1. a selective hydrocatalyst, take macroporous aluminium oxide as carrier, active metal component is palladium, and adjuvant component is Mo and/or W, and active metal component and adjuvant component are eggshell type at carrier surface and distribute, shell thickness is 0.05～0.20mm, the weight of catalyst of take is benchmark, and the content of active metal component Pd is 0.1%～0.5%, and the content of auxiliary agent Mo and/or W is 2.0%～10.0%, macroporous aluminium oxide content is 60%～90%, and the content of adhesive is 5%～30%; Described macroporous aluminium oxide has following character: specific area is 300～500m
2/ g, pore volume is 0.8～1.5mL/g, bore dia is that the shared pore volume of 10～20nm is total pore volume 50%～70%.
2. according to catalyst claimed in claim 1, it is characterized in that described macroporous aluminium oxide has following character: specific area is 400～500m
2/ g, pore volume is 0.9～1.5mL/g, bore dia is that the shared pore volume of 10～20nm is total pore volume 55%～70%.
3. according to catalyst claimed in claim 1, it is characterized in that the character of described catalyst is as follows: specific area is 150～280m
2/ g, pore volume is 0.7～1.0mL/g.
4. the preparation method of the arbitrary described catalyst of claim 1～3, comprise: to adding adhesive, peptizing agent kneading in macropore aluminium hydroxide, roll agglomerating after, through moulding, drying and roasting, obtain macroporous aluminium oxide, then supported active metal component and adjuvant component, drying and roasting, obtain selective hydrocatalyst again; Wherein, the preparation process of described macropore aluminium hydroxide, comprise the steps:
A, the first sodium aluminate solution is joined in plastic cans, ventilate simultaneously and pass into CO
2gas, control pH value to 11.0～13.0, and the neutralization reaction time is 1～2 hour;
B, then increase CO
2addition, add the second sodium aluminate solution in the material of step a gained, controlling the pH value constant is 8.0～11.0, adds simultaneously and accounts for 3%～5% the high molecular surfactant of step e gained aluminium hydroxide in aluminium oxide weight, and the neutralization reaction time is 0.5～1.0 hour;
C, at the control temperature and pH value of step b, said mixture ventilates and to stablize 1～3 hour;
D, the solidliquid mixture of step c gained is filtered and washs;
The solids drying of e, steps d gained obtains macropore aluminium hydroxide;
Wherein step a control reaction temperature is 20～40 ℃, and in step a, the concentration of the first sodium aluminate solution used is 15～60gAl
2o
3/ L, in step b, the concentration of the second sodium aluminate solution used is 15～60gAl
2o
3/ L, the addition of the first sodium aluminate solution accounts for the gross weight of the first sodium aluminate solution and the second sodium aluminate solution and counts 30%～50% with aluminium oxide;
The described high molecular surfactant of step b is one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, AEO, fatty alkanol amide and polyacrylamide, and the molecular weight of above-mentioned high molecular surfactant is 1.8～2.3 ten thousand; Step b controls constant pH value and controls the pH value low 0.3～4.0 of reaction end than step a.
5. the concentration that in accordance with the method for claim 4, it is characterized in that the first sodium aluminate solution used in step a is 20～40gAl
2o
3/ L, in step b, the concentration of the second sodium aluminate solution used is 20～40gAl
2o
3/ L.
6. in accordance with the method for claim 4, it is characterized in that described CO
2the concentration of gas is 10v%～60v%.
7. in accordance with the method for claim 4, it is characterized in that the described washing of steps d is to be washed till neutrality by the deionized water of 40～90 ℃; The described drying condition of step e is 110～130 ℃ of dryings 4～10 hours.
8. in accordance with the method for claim 4, it is characterized in that, the pH value that step a controls reaction end is 11.5～12.0, and it is 10.0～11.0 that step b controls the pH value constant.
9. according to the described method of claim 4 or 8, it is characterized in that step b controls constant pH value and controls the pH value low 1.0～2.0 of reaction end than step a.
10. in accordance with the method for claim 4, it is characterized in that described adhesive is little porous aluminum oxide.
11. in accordance with the method for claim 4, it is characterized in that the drying condition after described carrier moulding is as follows: 80～120 ℃ of dryings 2～15 hours, roasting condition was as follows: 900～1200 ℃ of roastings 4～8 hours.
12. in accordance with the method for claim 4, the load that it is characterized in that described active metal component and adjuvant component adopts following process: alumina support sprays the maceration extract containing palladium, then 100～130 ℃ of dryings 6～14 hours, 450～550 ℃ of roastings 5～10 hours, obtain the palladium-containing catalyst intermediate, adopt again the method sprayed will spray containing the maceration extract of Mo and/or W on the palladium-containing catalyst intermediate, then through 100～130 ℃ of dryings 6～14 hours, 500～600 ℃ of lower roastings 5～10 hours, obtain selective hydrocatalyst.
13. the arbitrary described catalyst of claim 1～3 is at drippolene C
9application in the cut fraction section selective hydrogenation process.
14. according to the described application of claim 13, it is characterized in that drippolene C
9the operating condition of cut fraction section selective hydrogenation is as follows: reaction temperature is 70～170 ℃, reaction pressure 1.0～4.0MPa, hydrogen to oil volume ratio 300～500, volume space velocity 1.0～3.0h during liquid
-1.
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| CN104162436B (en) * | 2013-05-20 | 2016-03-23 | 中国石油化工股份有限公司 | A kind of hydrogenation activity guard catalyst and preparation and application thereof |
| CN105903468B (en) * | 2016-04-22 | 2018-10-16 | 大连理工大学 | A kind of preparation method and applications for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil |
| CN107185536B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of catalyst and preparation method of diene hydrogenation |
| CN107163979B (en) * | 2017-06-02 | 2019-01-22 | 钦州学院 | A method of for diene hydrogenation |
| 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 |
| CN110038583B (en) * | 2018-01-16 | 2021-11-09 | 中国石油化工股份有限公司 | Preparation method of hydrofining catalyst |
| CN111375451B (en) * | 2018-12-29 | 2022-12-13 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst |
| KR102220225B1 (en) * | 2019-06-21 | 2021-02-24 | 희성촉매 주식회사 | A catalyst for preparing H2O2 and regenerating working solution and a method therefor |
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