CN102451685A - Selective hydrogenation catalyst and preparation method thereof - Google Patents
Selective hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102451685A CN102451685A CN2010105144913A CN201010514491A CN102451685A CN 102451685 A CN102451685 A CN 102451685A CN 2010105144913 A CN2010105144913 A CN 2010105144913A CN 201010514491 A CN201010514491 A CN 201010514491A CN 102451685 A CN102451685 A CN 102451685A
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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
With lighter hydrocarbons, naphtha, diesel oil or heavy oil is raw material, and Pintsch process is produced in the process of ethene in the presence of steam, generates the above liquid by-product of carbon containing five hydro carbons, and to do be that 205 ℃ liquid is called drippolene through fractionating out.Cracking of ethylene C
9Cut is to isolate C by drippolene through extracting
5Cut, C
6～C
8Residue cut behind the cut accounts for 10%～20% of ethene total output.
Along with increasing suddenly 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.And be that the hydrogen addition technology of core is an important branch in the field of hydrogenation with the pyrolysis gasoline hydrogenation catalyst, in the post processing of preparing ethylene by steam cracking technology, occupy very important position.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.
Industry at present goes up that pyrolysis gasoline hydrogenation catalyst mainly contains palladium system and nickel is two kinds of catalyst, but still is main with palladium series catalyst.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 big, and catalyst life is long.But owing to receive the influence of ethylene raw diversification, cut is laid particular stress in recent years, and 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
3Be carrier, palladium-impregnated content is that 0.15wt%～0.24wt% processes catalyst.CN1435277A discloses a kind of process for prepairng hydrogen peroxide by anthraquinone load type palladium-aluminium oxide catalyst and preparation method thereof that is used for, 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
3Be carrier, palladium-impregnated content is that 0.15wt%～0.25wt% processes catalyst.CN85100761A discloses a kind of fiber catalyst carrier that is used 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 colloid in the raw material of pyrolysis gasoline hydrogenation device etc. exceeded standard, pore volume was prone to coking and blocking on the catalyst, influences the catalyst hydrogenation stability.
US 3,898, and 298 disclose a kind of precious metals pd catalyst, it be with content be the Pd of 0.05wt%～0.2wt% as active component, aluminium oxide is a carrier, this hydrogenation catalyst only is applicable to the C of alkynes content low (below the 1.0wt%)
4The selective hydrogenation of cut.
CN101433841A discloses a kind of selective hydrocatalyst, is carrier with the aluminium oxide, 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 are the θ type or are master's θ, α mixing crystal formation with the θ type.This catalyst is fit to the full cut of drippolene, and for heavier cut, because specific area and pore volume are relatively low, influences activity of such catalysts and selectivity, and the catalyst rapid deactivation, the poor stability of catalyst, and 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 bigger pore volume and specific area, and strong anticol mass-energy power is arranged, and activity of such catalysts and selectivity are high, and good stability is specially adapted to drippolene C
9In the hydrogenation process of cut.
Selective hydrocatalyst of the present invention is a carrier with the macroporous aluminium oxide, and active metal component is a 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; Weight with catalyst 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 following: specific area is 150～280m
2/ g, pore volume are 0.7～1.0ml/g.
Described macroporous aluminium oxide has following character: specific area is 300～500m
2/ g, pore volume are 0.8～1.5ml/g, bore dia be the pore volume of 10～20nm account for total pore volume 50%～70%, preferred property is following: specific area is 400～500m
2/ g, pore volume are 0.9～1.5ml/g, and bore dia is that the shared pore volume of 10～20nm is 55%～70% of total pore volume.
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.
Preparation of catalysts method of the present invention is following: in macropore aluminium hydroxide, add adhesive, peptizing agent mix pinch, roll agglomerating after; Through moulding, drying and roasting; Obtain alumina support; Supported active metal component and adjuvant component through drying and roasting, obtain selective hydrocatalyst more then; Wherein, the preparation process of described macropore aluminium hydroxide comprises the steps:
A, first kind of sodium aluminate solution joined in the glue jar, ventilate simultaneously and feed CO
2Gas, control pH value to 11.0～13.0, the neutralization reaction time is 1～2 hour;
B, increase CO then
2Addition; In the material of step a gained, add second kind of sodium aluminate solution; Control pH value is constant to be 8.0～11.0, and adding simultaneously accounts for 3%～5% 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, under 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 washing;
The solids of e, steps d gained obtains macropore aluminium hydroxide through drying.
Among the step a, the concentration of first kind of sodium aluminate solution is 15～60gAl
2O
3/ l is preferably 20～40gAl
2O
3/ l.Among the step b, the concentration of second kind of sodium aluminate solution is 15～60gAl
2O
3/ l is preferably 20～40gAl
2O
3/ l.Wherein, first kind of sodium aluminate solution can adopt identical concentration with second kind of sodium aluminate solution, also can adopt different concentration.
Step a control reaction temperature is 20～40 ℃.
Described CO
2The concentration of gas is 10v%～60v%.
In the inventive method, the addition of first kind of sodium aluminate solution accounts for the gross weight of first kind of sodium aluminate solution and second kind of sodium aluminate solution and counts 30%～50% with aluminium oxide.
Step b, described high molecular surfactant be polyethylene glycol, gather in propyl alcohol, polyvinyl alcohol, AEO, fatty alkanol amide and the polyacrylamide one or more, and the molecular weight of above-mentioned high molecular surfactant is 1.8～2.3 ten thousand.
Increase CO described in the 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 with 40～90 ℃ deionized water; The described drying condition of step e is 110～130 ℃ of dryings 4～10 hours.
In the preparation of aluminium hydroxide process involved in the present invention, first kind of sodium aluminate solution neutralization reaction pH value controls to 11.0～13.0, is preferably 11.5～12.0, second kind of sodium aluminate solution and CO
2PH value in reaction is general constant to be 8.0～11.0, is preferably 10.0～11.0.The constant pH value of step b control hangs down 0.3～4.0 than the pH value of step a control reaction end, 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 like in nitric acid, hydrochloric acid, formic acid, acetate, the citric acid one or more, the addition of peptizing agent accounts for 0.5%～10.0% of catalyst weight.In the carrier forming process, can also add extrusion aid as required, such as the sesbania powder.
Described carrier moulding is looked different demands and can be made into different shape, and for example spherical, tablet, annular, hollow cylinder or bar shaped etc. better are bar shaped (clover, bunge bedstraw herb, cylinder bars etc.), are preferably the cylinder bar of 3～8 millimeters of diameters.Drying condition after the carrier moulding is following: 80～120 ℃ of dryings 2～15 hours, roasting condition was following: 900～1200 ℃ of roastings 4～8 hours.
Among the present invention, routine techniques is adopted in the load of active metal component and adjuvant component, such as immersion process for preparing; Preferably adopt the method that sprays, active metal component adopts the method for flooding respectively to load on the alumina support with adjuvant component, and is eggshell and is distributed on the carrier surface; Detailed process is following: alumina support sprays the maceration extract that contains palladium; At 100～130 ℃ of dry 6-14 hours,, obtain the palladium-containing catalyst intermediate then 450～550 ℃ of roastings 5～10 hours; The maceration extract that adopts the method that sprays will contain Mo and/or W again sprays on the palladium-containing catalyst intermediate; 100～130 ℃ of dryings of warp are 6～14 hours then, 500～600 ℃ of following roastings 5～10 hours, obtain selective hydrocatalyst.
The maceration extract that the present invention contains palladium can adopt conventional eggshell type to contain the method preparation of palladium maceration extract; Specific as follows: the palladium content that takes by weighing aequum is no less than the palladium bichloride powder of 59wt%; Add entry, add hydrochloric acid again, the dilution of dissolving back; Regulate the pH value according to required shell thickness, pH value scope is 3.0～6.0.
The maceration extract that the present invention contains Mo and/or W can adopt the conventional method preparation, and molybdenum salt and/or the tungsten salt that is about to solubility adds in the entry dissolving and gets.
Selective hydrocatalyst of the present invention is applicable to medium-low distillate oil selection 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 following: 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 used macropore aluminium hydroxide of the inventive method is to adopt a part of sodium aluminate change pH values, the method preparation that the permanent pH value of a part of sodium aluminate single current is heavy altogether, not only process is simple, and is easy to control, adopts CO simultaneously
2Stir with wind, make the full and uniform mixing of reactant.In becoming the glue process, lack part sodium aluminate change pH values, form the hole of inhomogeneous dispersion, strengthen CO afterwards
2Amount adds another part sodium aluminate fast under the condition of constant lower pH value, the pH value of follow-up one-tenth glue process is lower; The small structure that makes previous generation is peptization again, and follow-up colloid is generated rapidly equably, and adds surfactant simultaneously; Not only played the effect of expanding agent; And surfactant is embedded in the reaction structure and surface hydroxyl interacts, and has increased the specific area and the material dispersed property of carrier; 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 helps the growth of particle species simultaneously, thereby makes alumina support have bigger specific area and pore volume, and the aperture of pore distribution concentration is bigger.
Alumina support that the present invention adopts has bigger specific area and pore volume, and the aperture of pore distribution concentration is bigger, is not merely reactant enough passages are provided; Help the turnover of reactant and product, effectively avoided the polymerization of unsaturated hydrocarbons, block the duct; Bigger space and specific area bearing metal also is provided in addition; Make hydrogenation metal have higher dispersiveness, make catalyst of the present invention not only have suitable activity, have more high hydrogenation selectivity.Because active component palladium and C
9Unsaturated hydrocarbons in the cut is prone to complex reaction takes place, and palladium is run off gradually, thereby cause catalysqt deactivation.The promoter metal of adding among the present invention can and active component palladium between produce to interact; And help the even distribution of palladium particle, also can strengthen the interaction between palladium and carrier simultaneously, thereby reduce the loss of palladium; Improve the utilization rate of palladium, prolong catalyst service life.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.Among the present invention, wt% is a mass fraction, and v% is a volume fraction.
Among 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 concentration
2O
3The dense sodium aluminate solution of/l, being diluted to concentration again is 25gAl
2O
3/ L and 35gAl
2O
3/ L sodium aluminate working solution is got the steel of a 30L and is processed the glue jar, adds 5L earlier and contains 25gAl
2O
3/ L sodium aluminate working solution ventilates simultaneously and feeds the CO that concentration is 45v%
2Gas, 25 ℃ of reaction temperatures, the reaction time is 1 hour, the pH value was adjusted CO rapidly by 11.5 o'clock
2Flow, add 8.3L and contain 35gAl
2O
3The sodium aluminate working solution of/L adds the 17g molecular weight and is 20,000 polyethylene glycol simultaneously, and the pH of system is remained on about 10.0,25 ℃ of reaction temperatures, and the reaction time is 1 hour, after question response is intact, stops to feed CO
2, ventilating then and stablized 60 minutes, dope filtration also is washed till neutrality with 60 ℃ of deionized waters, 120 ℃ of dryings 8 hours, obtains macropore aluminium hydroxide Y-1 then.Through 550 ℃ of roastings 5 hours, obtain macroporous aluminium oxide A-1, its character is seen table 1.
Embodiment 2
It is 200gAl that solid sodium aluminate is mixed with concentration
2O
3The dense sodium aluminate solution of/l, being diluted to concentration again is 25gAl
2O
3/ L sodium aluminate working solution is got the steel of a 30L and is processed the glue jar, adds 5L earlier and contains 25gAl
2O
3/ L sodium aluminate working solution ventilates simultaneously and feeds the CO that concentration is 40v%
2Gas, 25 ℃ of reaction temperatures, the reaction time is 1.2 hours, the pH value was adjusted CO rapidly by 12.0 o'clock
2Flow, add 11L and contain 25gAl
2O
3The sodium aluminate working solution of/L adds the 21g molecular weight and is 20,000 polyethylene glycol simultaneously, and the pH of system is remained on about 10.0,25 ℃ of reaction temperatures, and the reaction time is 0.8 hour, after question response is intact, stops to feed CO
2, ventilating then and stablized 60 minutes, dope filtration also is washed till neutrality with 60 ℃ of deionized waters.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 seen 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 of 4g and mix and to pinch, roll, but process the paste of extrusion, extruded moulding, 110 ℃ of dryings 2 hours, 1000 ℃ of roastings 4 hours make carrier A.
Take by weighing 0.5g palladium content and be no less than the palladium bichloride powder of 59wt%, add entry, add hydrochloric acid again, be diluted to 80ml after the dissolving, regulate pH value to 3.5; Take by weighing the 100g carrier A, the palladium chloride solution for preparing is sprayed on the carrier A, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours make catalyst intermediate TA.
Take by weighing ammonium heptamolybdate 3.7g, be configured to the 80ml aqueous solution, spray on the above-mentioned catalyst intermediate TA, 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 of 2.7g and mix and to pinch, roll, but process the paste of extrusion, extruded moulding, 110 ℃ of dryings 2 hours, 1000 ℃ of roastings 4 hours make carrier B.
Take by weighing 0.8g palladium content and be no less than the palladium bichloride powder of 59wt%, add entry, add hydrochloric acid again, be diluted to 80ml after the dissolving, regulate pH value to 4.0; Take by weighing the 100g carrier B, the palladium chloride solution for preparing is sprayed on the carrier B, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours make catalyst intermediate TB.
Take by weighing ammonium metatungstate 3.9g, be configured to the 80ml aqueous solution, spray on the above-mentioned catalyst intermediate TB, 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 concentration
2O
3The dense sodium aluminate solution of/l, being diluted to concentration again is 35gAl
2O
3/ L sodium aluminate working solution (a) is got the steel of a 30L and is processed the glue jar, opens the container valve that has (a), ventilates simultaneously and feeds the CO that concentration is 45v%
2Gas, the flow of setting (a) makes the reaction time at 1 hour, and adjusts CO rapidly
2Flow, the pH of system is remained on about 10.0,25 ℃ of reaction temperatures, treat that (a) reacted after, stop to feed CO
2, dope filtration also is washed till neutrality with 60 ℃ of deionized waters.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 seen 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 of 4g and mix and to pinch, roll, but process the paste of extrusion, extruded moulding.110 ℃ of dryings 2 hours, 1000 ℃ of roastings 4 hours make carrier DA.
Take by weighing 0.5g palladium content and be no less than the palladium bichloride powder of 59wt%, add entry, add hydrochloric acid again, be diluted to 80ml after the dissolving, regulate the pH value according to required shell thickness; Take by weighing 100g carrier DA, the palladium chloride solution for preparing is sprayed on the carrier DA, 120 ℃ of oven dry in air, 500 ℃ of roastings 4 hours make catalyst intermediate DTA.
Take by weighing ammonium molybdate 3.7g, be configured to the 80ml aqueous solution, spray on the catalyst intermediate DTA, 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 |
Can find out that from table 2 comparative example carrier and catalyst pore volume, specific surface and aperture are all lower, can influence metal undoubtedly and get decentralization, can not influence the turnover of reactant and product for reactant provides enough passages in addition.The invention described above catalyst and comparative example catalyst are carried out active evaluation test.Characterize activity of such catalysts with the diene content that generates oil.
Embodiment 5
Test is with raw material cracking of ethylene C
9Cut, test use hydrogen to cross as deoxidation and through silica gel-molecular sieve dehydration purified treatment, and the electrolysis hydrogen of hydrogen purity＞99v% adopts 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 seen table 3.
Embodiment 6
The evaluate catalysts process is with embodiment 5, and evaluate catalysts is catB, and products obtained therefrom character is seen table 3.
Comparative example 3
The evaluate catalysts process is with embodiment 5, and evaluate catalysts is DcatA, and products obtained therefrom character is seen 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 |
| Take off the diene rate, wt% | - | 86.58 | 85.37 | 71.95 |
| Liquid is received, wt% | - | 100.11 | 100.08 | 99.74 |
Visible by table 3, adopt the catA catalyst, the diene content of hydrogenated products descends significantly, takes off the diene rate and reaches 86.58%, and iodine number is reduced to 45.3gI/100ml by 97.1gI/100ml, and existent gum is reduced 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; Take off diene rate 71.95%; Iodine number is reduced to 70.7gI/100m by 97.10gI/100ml, and existent gum is reduced to 78mg/100ml by 80mg/100ml, has proved absolutely that selective hydrocatalyst of the present invention has stronger hydrogenation activity and selectivity.
Claims (20)
1. a selective hydrocatalyst is a carrier with the macroporous aluminium oxide, and active metal component is a 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; Weight with catalyst is benchmark, and the content of active metal component Pd is 0.1%～0.5%, and the content of auxiliary agent Mo and/or Co is 2.0%～10.0%; Macroporous aluminium oxide content is 60%～90%, and the content of adhesive is 5%～30%.
2. according to the described catalyst of claim 1, it is characterized in that described macroporous aluminium oxide has following character: specific area is 300～500m
2/ g, pore volume are 0.8～1.5ml/g, and bore dia is that the shared pore volume of 10～20nm is 50%～70% of total pore volume.
3. according to the described catalyst of claim 1, it is characterized in that described macroporous aluminium oxide has following character: specific area is 400～500m
2/ g, pore volume are 0.9～1.5ml/g, and bore dia is that the shared pore volume of 10～20nm is 55%～70% of total pore volume.
4. according to the described catalyst of claim 1, it is characterized in that the character of said catalyst is following: specific area is 150～280m
2/ g, pore volume are 0.7～1.0ml/g.
5. the arbitrary said Preparation of catalysts method of claim 1～4; Comprise: in macropore aluminium hydroxide, add adhesive, peptizing agent mix pinch, roll agglomerating after; Through moulding, drying and roasting, obtain alumina support, then supported active metal component and adjuvant component; Through drying and roasting, obtain selective hydrocatalyst again; Wherein, the preparation process of described macropore aluminium hydroxide comprises the steps:
A, first kind of sodium aluminate solution joined in the glue jar, ventilate simultaneously and feed CO
2Gas, control pH value to 11.0～13.0, the neutralization reaction time is 1～2 hour;
B, increase CO then
2Addition; In the material of step a gained, add second kind of sodium aluminate solution; Control pH value is constant to be 8.0～11.0, and adding simultaneously 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, under 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 washing;
The solids of e, steps d gained obtains macropore aluminium hydroxide through drying.
6. according to the described method of claim 5, it is characterized in that step a control reaction temperature is 20～40 ℃.
7. according to the described method of claim 5, the concentration that it is characterized in that first kind of used among step a sodium aluminate solution is 15～60gAl
2O
3/ l, the concentration of second kind of used sodium aluminate solution is 15～60gAl among the step b
2O
3/ l.
8. according to the described method of claim 5, the concentration that it is characterized in that first kind of used among step a sodium aluminate solution is 20～40gAl
2O
3/ l, the concentration of second kind of used sodium aluminate solution is 20～40gAl among the step b
2O
3/ l.
9. according to the described method of claim 5, it is characterized in that described CO
2The concentration of gas is 10v%～60v%.
10. according to the described method of claim 5, it is characterized in that the addition of first kind of sodium aluminate solution accounts for the gross weight of first kind of sodium aluminate solution and second kind of sodium aluminate solution and counts 30%～50% with aluminium oxide.
11. according to the described method of claim 5; It is characterized in that the described high molecular surfactant of step b is polyethylene glycol, gathers in propyl alcohol, polyvinyl alcohol, AEO, fatty alkanol amide and the polyacrylamide one or more, the molecular weight of above-mentioned high molecular surfactant is 1.8～2.3 ten thousand.
12., it is characterized in that the described washing of steps d is to be washed till neutrality with 40～90 ℃ deionized water according to the described method of claim 5; The described drying condition of step e is 110～130 ℃ of dryings 4～10 hours.
13., it is characterized in that the pH value of step a control reaction end is 11.5～12.0 according to the described method of claim 5, step b control pH value is constant to be 10.0～11.0.
14., it is characterized in that the pH value low 0.3～4.0 of the constant pH value of step b control than step a control reaction end according to the described method of claim 5.
15., it is characterized in that the pH value low 1.0～2.0 of the constant pH value of step b control than step a control reaction end according to claim 5 or 13 described methods.
16., it is characterized in that described adhesive is little porous aluminum oxide according to the described method of claim 5.
17. according to the described method of claim 5, it is characterized in that the drying condition after the described carrier moulding is following: 80～120 ℃ of dryings 2～15 hours, roasting condition was following: 900～1200 ℃ of roastings 4～8 hours.
18. according to the described method of claim 5; Following process is adopted in the load that it is characterized in that described active metal component and adjuvant component: alumina support sprays the maceration extract that contains palladium; 100～130 ℃ of dryings 6～14 hours,, obtain the palladium-containing catalyst intermediate then 450～550 ℃ of roastings 5～10 hours; The maceration extract that adopts the method that sprays will contain Mo and/or W again sprays on the palladium-containing catalyst intermediate; 100～130 ℃ of dryings of warp are 6～14 hours then, 500～600 ℃ of following roastings 5～10 hours, obtain selective hydrocatalyst.
19. the arbitrary described catalyst of claim 1～4 is at drippolene C
9Application in the cut fraction section selective hydrogenation process.
20., it is characterized in that drippolene C according to the described application of claim 19
9The operating condition of cut fraction section selective hydrogenation is following: 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
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