CN103386302B - Petroleum resin hydrogenation catalyst and preparation method thereof - Google Patents

Petroleum resin hydrogenation catalyst and preparation method thereof Download PDF

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CN103386302B
CN103386302B CN201310316203.7A CN201310316203A CN103386302B CN 103386302 B CN103386302 B CN 103386302B CN 201310316203 A CN201310316203 A CN 201310316203A CN 103386302 B CN103386302 B CN 103386302B
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catalyst
palladium
carrier
preparation
hydrogenation
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CN103386302A (en
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王继元
堵文斌
许建文
卞伯同
陈韶辉
杨爱武
柏基业
朱庆奋
庞焱
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention provides a petroleum resin hydrogenation catalyst and a preparation method thereof. The petroleum resin hydrogenation catalyst comprises an Al2O3 carrier, a precious metal Pd loaded on the Al2O3 and an assistant element oxide. The catalyst provided by the invention has high activity, and the steeping depth of active metals in the catalyst is controllable; and the preparation method of the catalyst is simple and suitable for industrial production.

Description

A kind of hydrogenation of petroleum resin Catalysts and its preparation method
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method thereof, particularly relate to a kind of C9 hydrogenation of petroleum resin Catalysts and its preparation method.
Background technology
C9 Petropols are the thermoplastic resins utilizing the C9 cut of cracking ethylene by-product to carry out being polymerized a kind of undefined structure obtained, and finished product presents yellow to light brown, have good pour point depression and increase stickiness energy, dissolve in benzene,toluene,xylene equal solvent.The shortcomings such as containing higher unsaturated double-bond in the polymer chain of C9 Petropols, therefore there is color dark, thermo oxidative stability is low, cohesiveness difference, usually need hydrogenation to obtain shallow white or to connect subdiaphanous hydrogenation resin.
C9 Petropols molecule is chain and circulus, greatly sterically hindered, and unsaturated bond hydrogenation reaction activation energy is high, and hydroconversion condition is harsh, and hydrogenation reaction needs to carry out under high temperature, high pressure and high activated catalyst condition.The preparation of prior art hydrogenation C9 Petropols is dissolved in suitable solvent by C9 Petropols, and under supported palladium or Raney nickel effect, under uniform temperature and pressure, carry out hydrogenation reaction, thick product obtains hydrogenation C9 petroleum resin products after solvent recovery.
Concrete such as Chinese patent CN1962706 (a kind of preparation method of hydrogenation C5/C9 copolymerized petroleum resin) prior art Problems existing is that catalyst life is short, and product colour can not meet the needs of reality.
In order to improve the life-span of C 9 petroleum resin hydrogenation catalyst, there is carried noble metal hydrogenation catalyst, such as Chinese patent CN102002130 (a kind of preparation method of hydrogenated carbon 9 petroleum resin) discloses a kind of preparation method of carried noble metal hydrogenated carbon 9 petroleum resin catalyst, first carry out the preparation of alumina support, again palladium and platinum, transition metal active component are coated on alumina support, activatedly obtain hydrogenation catalyst.High-pressure hydrogenation reaction temperature is 250 ~ 350 DEG C, and pressure is 8 ~ 20MPa, and liquid volume air speed is 0.5 ~ 2h -1, the colourity of final hydrogenated carbon 9 petroleum resin number≤1#, softening point>=100 DEG C.US Patent No. 20050228143 (catalyst for petroleum resin hydrogenation and process for producing hydrogenated petroleumresin) discloses a kind of noble metal catalyst for the process of sulfur-bearing C9 hydrogenation of petroleum resin, in catalyst, the mass ratio of Pd/Pt is 2.5 ~ 3.5/1, and catalyst has higher catalytic activity and stability.(the color improvment of C9hydrocarbon resin by hydrogenation over2%Pd/ γ-Alumina catalyst:effect of degree of aromatic rings hydrogenation.Journal of Applied Polymer Science such as Sae-Ma, 2010,117:2862 – 2869) report the method for hydrotreating of light C9 Petropols.C9 Petropols are dissolved in cyclohexane solvent by they, with 2%Pd/ γ-Al 2o 3for catalyst, under the reaction condition of temperature 250 DEG C, pressure 7MPa, investigate the relation of C9 hydrogenation of petroleum resin degree and colourity number.Colourity number without the C9 Petropols (p-C9HR) of hydrotreatment is 17.1#; Hydrogenation degree is the colourity number of the C9 Petropols of 50% is 8.8#; Hydrogenation degree is the colourity number of the C9 Petropols of 90% is 6#.Load type palladium system and palladium-platinum group catalyst solve the dark problem of hydrogenation resin product color, weak point is the easy carbon distribution inactivation of the noble-metal-supported degree of depth and the inadequate catalyst of decentralization, and the life-span can not meet real industrial requirement.
For the noble metal catalyst of C9 hydrogenation of petroleum resin, require that the noble metal of load is distributed in the certain depth of carrier surface, but it is dark to distribute as far as possible, and requires that the decentralization of carried metal will be got well, the performance of catalyst could be played best.The catalyst of these prior aries exists and conscientiously cannot meet actual needs, there is the leeway needing to improve further.
Therefore, the present situation of prior art is, a kind of activity of needs exploitation is high, noble metal distributes rational C9 hydrogenation of petroleum resin catalyst, and in catalyst, the content of crystallite of metal Pd is high, good dispersion, and the activity of catalyst is high.Its two, in catalyst, the impregnating depth of precious metals pd is controlled.Its three, the preparation method of catalyst is simple, and suitability for industrialized is produced.
Summary of the invention
The present inventor passes through to adopt K on prior art basis 2o is to Al 2o 3carrier is modified, and carried noble metal, well solve foregoing problems, complete the present invention.Specifically, the present invention relates to following content:
1, a hydrogenation of petroleum resin catalyst, is characterized in that: comprise Al 2o 3carrier, be carried on Al 2o 3on precious metals pd and auxiliary element oxide, in described catalyst, the load depth of precious metals pd is 1 ~ 100 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for more than 90% of palladium crystal grain sum.Wherein said auxiliary element oxide is selected from K 2o, TiO 2.
2, the catalyst of any preceding aspect, in described catalyst, the load depth of precious metals pd is 1 ~ 100 μm, and preferred load depth is 1 ~ 50 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for more than 90% of palladium crystal grain sum.
3, above-mentioned hydrogenation catalyst, based on the gross mass of described catalyst, the content of described Pd is 0.5 ~ 5%, is preferably 0.5 ~ 2%, K 2o is 0.1 ~ 5%, is preferably 0.1 ~ 1%, TiO 2be 1 ~ 10%, be preferably 1 ~ 5%, remainder is Al 2o 3.
The preparation method of 4, above-mentioned hydrogenation catalyst, is characterized in that comprising the following steps:
(1) by Al 2o 3the solution of carrier impregnation sylvite, obtains K through 100 DEG C of dryings and 300 ~ 600 DEG C of roasting 4h 2o/Al 2o 3carrier;
(2) by nanoscale titanium hydroxide and join in deionized water containing palladium compound, in the process stirred, drip nitric acid adjust ph is 0.5 ~ 5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3colloidal sol 0.1 ~ the 1h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dryings, 200 ~ 400 DEG C of roasting 4h, 50 ~ 200 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
Above-mentioned hydrogenation catalyst, described Al 2o 3the specific area of carrier is 50 ~ 200m 2/ g, pore volume is 0.3 ~ 1.0cm 3/ g, average pore size is 10 ~ 100nm.
Above-mentioned hydrogenation catalyst, described Al 2o 3the shape of carrier is multiple, such as in powder, spherical, sheet, cylindric, clover, bunge bedstraw herb, the shape such as honeycomb.
The preparation method of above-mentioned hydrogenation catalyst, the sylvite described in step (1) is selected from any one or its combination in potassium nitrate, potassium hydroxide, potash or saleratus.
The preparation method of above-mentioned hydrogenation catalyst, the sintering temperature described in step (1) 300 ~ 600 DEG C.
The preparation method of above-mentioned hydrogenation catalyst, nanoscale titanium hydroxide described in step (2) is known by the art those of ordinary skill, is normally prepared by method for hydrolysis by any one in titanium tetrachloride, butyl titanate, isopropyl titanate.
The preparation method of above-mentioned hydrogenation catalyst, described in step (2) is any one or its combination in palladium dydroxide, palladium bichloride, palladium, palladium nitrate, dichloro four ammonia palladium or ammonium chloropalladate containing palladium compound.
Hydrogenation catalyst of the present invention, the mass content of described each component is the standard test adopting RIPP128-90 on U.S. Jarrell-Ash company J-A1100 type ICP; Described Al 2o 3the specific area of carrier, pore volume and average pore size measure on U.S. Micromeritics company ASAP2010 physical adsorption appearance; The ratio that described Metal Palladium crystallite accounts for palladium crystal grain sum observes at least 200 Metal Palladium crystal grain on Jeol Ltd. JEOL2010 type transmission electron microscope, calculates according to statistical method.
Hydrogenation catalyst of the present invention, the activity rating of described catalyst carries out on continuous fixed bed reactors.The C9 Petropols of employing colourity 10#, softening point 115 DEG C are raw material, be dissolved in cyclohexane solvent, be made into the solution that mass concentration is 10% by C9 Petropols.Loaded catalyst 10ml is 280 DEG C in reaction temperature, and pressure is 7MPa, and liquid hourly space velocity (LHSV) is 1h -1, carry out hydrogenation reaction under the condition of hydrogen to oil volume ratio 500:1, product obtains hydrogenation C9 Petropols after solvent recovery.The colourity number of described C9 Petropols adopts iron-cobalt colorimetric method, with reference to the standard test of GB GB4317-84; The softening point of described C9 Petropols adopts ring and ball method, with reference to the standard test of GB GB4507-84.
Beneficial effect
The preparation method of C9 hydrogenation of petroleum resin catalyst of the present invention, adopts K 2o is to Al 2o 3carrier is modified, and is conducive to the anti-carbon deposition ability and the stability that improve catalyst.In the process for preparation of colloidal sol, be adsorbed on nanoscale titanium hydroxide colloid consumingly containing palladium compound, effectively can be regulated the impregnating depth of precious metals pd by the pH value controlling colloidal sol.Catalyst is after roasting, and metal Pd quilt " grappling " is at TiO 2on, Pd crystal grain be can effectively isolate, thus content and the dispersive property of metal Pd crystallite substantially increased.TiO 2existence, change the electronic environment around metal Pd, make catalyst have higher Hydrogenation, TiO 2can also barrier potential be formed, stop the migration of Pd crystal grain under pyroreaction condition and grow up, extending the service life of catalyst.
Compared with prior art, advantage of the present invention is: one, and in catalyst, the content of crystallite of metal Pd is high, good dispersion, and the activity of catalyst is high.Its two, in catalyst, the impregnating depth of precious metals pd is controlled.Its three, the preparation method of catalyst is simple, and suitability for industrialized is produced.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.
According to the present invention, described load depth refers to that active metal palladium is at carrier A l 2o 3the degree of depth of upper dipping, the load depth of described metal Pd measures on U.S. Physical electronics company Quantum2000 type X-ray scanning microprobe electron spectrometer.According to the present invention, a kind of hydrogenation of petroleum resin catalyst is provided, it is characterized in that: comprise Al 2o 3carrier, be carried on Al 2o 3on precious metals pd and auxiliary element oxide, in described catalyst, the load depth of precious metals pd is 1 ~ 100 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for more than 90% of palladium crystal grain sum.Wherein said auxiliary element oxide is selected from K 2o, TiO 2.
According to the present invention, auxiliary element exists in the catalyst in the form of the oxide, although may not be strict meet the aforementioned oxide chemistry formula provided, in order to characterize and measure needs, be expressed as described oxide;
According to the present invention, based on the gross mass of catalyst, in catalyst, the content of Pd is 0.5 ~ 5%, is preferably 0.5 ~ 2%, K 2o is 0.1 ~ 5%, is preferably 0.1 ~ 1%, TiO 2be 1 ~ 10%, be preferably 1 ~ 5%, remainder is Al 2o 3.
According to the present invention, containing poisonous or easily cause element such as chromium, the lead etc. of environmental pollution in described catalyst, therefore there is eco-friendly feature;
According to the present invention, by using auxiliary element, can effectively solve the catalyst activity Metal Supported degree of depth in prior art, decentralization not, the problem of poor catalyst activity, the catalyst of the final acquisition of inventing is made to show the impregnating depth of precious metals pd in catalyst controlled, noble metal distribution rationally, the feature that the activity of catalyst is high.Such as when using catalyst of the present invention to carry out hydrogenation of petroleum resin reaction, the activity of catalyst can make that the colourity of C9 Petropols number is down to 4# by 10#, softening point is down to 102 DEG C by 115 DEG C.
According to the present invention, described catalyst main component refers to that catalyst is except described Al 2o 3, outside precious metal palladium and described auxiliary agent metal oxides, can also containing the impurity inevitably introduced in catalyst preparation process or the inevitable accessory substance generated, generally speaking these impurity or by-products content are extremely low, do not produce substantial impact to the activation plays of catalyst.
According to the present invention, the preparation method of above-mentioned hydrogenation of petroleum resin catalyst is provided, it is characterized in that comprising the following steps:
(1) by Al 2o 3the solution of carrier impregnation sylvite, obtains K through 100 DEG C of dryings and 300 ~ 600 DEG C of roasting 4h 2o/Al 2o 3carrier;
(2) by nanoscale titanium hydroxide and join in deionized water containing palladium compound, in the process stirred, drip nitric acid adjust ph is 0.5 ~ 5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3colloidal sol 0.1 ~ the 1h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dryings, 200 ~ 400 DEG C of roasting 4h, 50 ~ 200 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
According to the present invention, described dip time is as the criterion to obtain uniform impregnation product, and such as the dip time of step (3) is 0.1 ~ 1h, is sometimes also not limited thereto.
According to the present invention, described adjust ph is 0.5 ~ 5 is with inorganic acid such as nitric acid, and to the concentration of acid, there is no particular restriction, as long as the sol pH of step (2) is adjusted to 0.5 ~ 5.PH value regulates affects the impregnating depth of Pd on carrier, but the present invention finds that load depth more than 100 μm, can not exceed the activity affecting catalyst, and load depth of the present invention is 1 ~ 100 μm, preferably 1 ~ 50 μm.
According to the present invention, adopt K 2o is to Al 2o 3carrier is modified, and by inference, final obtained catalyst has lower acidity, compared with prior art catalyst (such as Supported Pt Nanoparticles-palladium series catalyst), effectively can avoid carbon distribution and the deactivation prob of catalyst, demonstrate good heat-resisting quantity.
Embodiment 1
(1) be 100m by specific area 2/ g, pore volume is 0.5cm 3/ g, average pore size is the spherical Al of 50nm 2o 3the solution of carrier impregnation potassium nitrate, obtains K through 100 DEG C of dry 10h and 400 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide and palladium nitrate, in the process stirred, drip nitric acid adjust ph is 3, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 0.5h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 300 DEG C of roasting 4h, 100 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 2%, K 2o is 1%, TiO 2be 5%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 50 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 93% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 2# by 10#, softening point is down to 110 DEG C by 115 DEG C.
Embodiment 2
(1) be 50m by specific area 2/ g, pore volume is 0.3cm 3/ g, average pore size is the spherical Al of 100nm 2o 3the solution of carrier impregnation potassium hydroxide, obtains K through 100 DEG C of dry 10h and 300 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide and palladium dydroxide, in the process stirred, drip nitric acid adjust ph is 0.5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 1h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 200 DEG C of roasting 4h, 50 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 0.5%, K 2o is 0.1%, TiO 2be 1%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 100 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 94% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 4# by 10#, softening point is down to 112 DEG C by 115 DEG C.
Embodiment 3
(1) be 200m by specific area 2/ g, pore volume is 1.0cm 3/ g, average pore size is the spherical Al of 10nm 2o 3the solution of carrier impregnation potash, obtains K through 100 DEG C of dry 10h and 600 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide and palladium bichloride, in the process stirred, drip nitric acid adjust ph is 5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 0.1h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 400 DEG C of roasting 4h, 200 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 5%, K 2o is 5%, TiO 2be 10%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 1 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 90% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 2# by 10#, softening point is down to 100 DEG C by 115 DEG C.
Embodiment 4
(1) be 100m by specific area 2/ g, pore volume is 0.5cm 3/ g, average pore size is the spherical Al of 50nm 2o 3the solution of carrier impregnation saleratus, obtains K through 100 DEG C of dry 10h and 500 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide and palladium, in the process stirred, drip nitric acid adjust ph is 1, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 0.2h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 300 DEG C of roasting 4h, 100 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 1%, K 2o is 0.1%, TiO 2be 10%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 65 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 96% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 3# by 10#, softening point is down to 107 DEG C by 115 DEG C.
Embodiment 5
(1) be 80m by specific area 2/ g, pore volume is 0.4cm 3/ g, average pore size is the spherical Al of 70nm 2o 3the solution of carrier impregnation potassium nitrate, obtains K through 100 DEG C of dry 10h and 550 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide and dichloro four ammonia palladium, in the process stirred, drip nitric acid adjust ph is 4, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 0.8h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 350 DEG C of roasting 4h, 150 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 5%, K 2o is 5%, TiO 2be 1%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 82 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 91% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 2# by 10#, softening point is down to 103 DEG C by 115 DEG C.
Embodiment 6
(1) be 150m by specific area 2/ g, pore volume is 0.8cm 3/ g, average pore size is the spherical Al of 20nm 2o 3the combination solution of carrier impregnation potash and potassium hydroxide, obtains K through 100 DEG C of dry 10h and 400 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide and ammonium chloropalladate, in the process stirred, drip nitric acid adjust ph is 2.5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 0.2h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 300 DEG C of roasting 4h, 100 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 2%, K 2o is 2%, TiO 2be 4%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 25 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 95% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 1# by 10#, softening point is down to 104 DEG C by 115 DEG C.
Embodiment 7
(1) be 150m by specific area 2/ g, pore volume is 0.8cm 3/ g, average pore size is the spherical Al of 20nm 2o 3the combination solution of carrier impregnation potassium nitrate and potassium hydroxide, obtains K through 100 DEG C of dry 10h and 400 DEG C roasting 4h 2o/Al 2o 3carrier;
(2) join in deionized water by nanoscale titanium hydroxide, palladium dydroxide and palladium nitrate, in the process stirred, drip nitric acid adjust ph is 1.5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3the colloidal sol 0.6h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dry 10h, 300 DEG C of roasting 4h, 100 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
The catalyst that the present embodiment obtains has following performance: in catalyst, the mass content of each component is: Pd is 2%, K 2o is 4%, TiO 2be 8%, remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 75 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 94% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 1# by 10#, softening point is down to 105 DEG C by 115 DEG C.
Embodiment 8
Substantially the same manner as Example 1, but Al 2o 3the shape of carrier is Powdered.
Embodiment 9
Substantially the same manner as Example 1, but Al 2o 3the shape of carrier is sheet.
Embodiment 10
Substantially the same manner as Example 1, but Al 2o 3the shape of carrier is cylindric.
Embodiment 11
Substantially the same manner as Example 1, but Al 2o 3the shape of carrier is clover.
Embodiment 12
Substantially the same manner as Example 1, but Al 2o 3the shape of carrier is bunge bedstraw herb.
Embodiment 13
Substantially the same manner as Example 1, but Al 2o 3the shape of carrier is cellular.
Embodiment 14
Substantially the same manner as Example 1, but sylvite is the combination of potassium nitrate, potassium hydroxide and potash.
Embodiment 15
Substantially the same manner as Example 1, but contain the combination that palladium compound is palladium dydroxide, palladium and palladium nitrate.
Comparative example 1
This comparison example is compared with embodiment 1, and the method described according to Chinese patent CN102002131 (a kind of preparation method of high-quality hydrogenated carbon 9 petroleum resin) prepares C9 hydrogenation of petroleum resin catalyst.
Take boehmite as alumina raw material, with certain mass zinc oxide after kneading, extruded is the trifolium-shaped bar of external diameter 1.2mm, obtains catalyst carrier at 1000 DEG C of roasting 4h.Be that maceration extract floods carrier with the zinc nitrate solution of scheduled volume, then through 120 DEG C of dry 12h, 450 DEG C of roasting 4h, then the method supported active metals Pd adopting incipient impregnation, obtain the catalyst of this comparative example after 120 DEG C of oven dry, 450 DEG C of roastings, 150 DEG C of hydrogen reducings.
The activity rating of this comparative example catalyst is substantially the same manner as Example 1.
The catalyst that this comparative example obtains has following performance: in catalyst, the mass content of each component is: Pd is 2%, ZnO is 4%, and remainder is Al 2o 3.In catalyst, the load depth of precious metals pd is 450 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for 80% of palladium crystal grain sum.The activity of catalyst can make that the colourity of C9 Petropols number is down to 4# by 10#, softening point is down to 102 DEG C by 115 DEG C.
Comparative example 1 and embodiment 1 are contrasted, can find out, in catalyst prepared by the inventive method, the load depth of precious metals pd is more shallow, and the ratio that the Metal Palladium crystallite that particle diameter is less than 3nm accounts for palladium crystal grain sum is higher, and the colourity of C9 hydrogenation of petroleum resin product is more shallow, softening point is higher.

Claims (10)

1. a hydrogenation of petroleum resin catalyst, is characterized in that: comprise Al 2o 3carrier, be carried on Al 2o 3on precious metals pd and auxiliary element oxide, in described catalyst, the load depth of precious metals pd is 1 ~ 100 μm, and the Metal Palladium crystallite that particle diameter is less than 3nm accounts for more than 90% of palladium crystal grain sum, and wherein said auxiliary element oxide is selected from K 2o, TiO 2; Based on the gross mass of described catalyst, the content of described Pd is 0.5 ~ 5%, K 2o is 0.1 ~ 5%, TiO 2be 1 ~ 10%.
2. catalyst according to claim 1, is characterized in that: in described catalyst, the load depth of precious metals pd is 1 ~ 50 μm.
3. catalyst according to claim 1, is characterized in that: the application of described catalyst in hydrogenation of petroleum resin.
4. catalyst according to claim 1, is characterized in that: based on the gross mass of described catalyst, and the content of described Pd is 0.5 ~ 2%, K 2o is 0.1 ~ 1%, TiO 2be 1 ~ 5%.
5. the preparation method of catalyst according to claim 1, is characterized in that comprising the following steps:
(1) by Al 2o 3the solution of carrier impregnation sylvite, obtains K through 100 DEG C of dryings and 300 ~ 600 DEG C of roasting 4h 2o/Al 2o 3carrier;
(2) by nanoscale titanium hydroxide and join in deionized water containing palladium compound, in the process stirred, drip nitric acid adjust ph is 0.5 ~ 5, obtains transparent colloidal sol;
(3) by the K of step (1) gained 2o/Al 2o 3colloidal sol 0.1 ~ the 1h of carrier impregnation step (2), obtains Pd-TiO through 100 DEG C of dryings, 200 ~ 400 DEG C of roasting 4h, 50 ~ 200 DEG C of hydrogen reducing 2h after dipping terminates 2-K 2o/Al 2o 3catalyst.
6. preparation method according to claim 5, described Al 2o 3the specific area of carrier is 50 ~ 200m 2/ g, pore volume is 0.3 ~ 1.0cm 3/ g, average pore size is 10 ~ 100nm.
7. preparation method according to claim 5, described Al 2o 3the shape of carrier is powder, spherical, sheet, cylindric, clover, bunge bedstraw herb, honeycomb shape.
8. preparation method according to claim 5, the sylvite described in described step (1) is selected from any one or its combination in potassium nitrate, potassium hydroxide, potash or saleratus.
9. preparation method according to claim 5, the titanium hydroxide described in described step (2) is selected from nanoscale titanium hydroxide.
10. preparation method according to claim 5, any one or its combination be selected from containing palladium compound in palladium dydroxide, palladium bichloride, palladium, palladium nitrate, dichloro four ammonia palladium or ammonium chloropalladate described in described step (2).
CN201310316203.7A 2013-07-25 2013-07-25 Petroleum resin hydrogenation catalyst and preparation method thereof Active CN103386302B (en)

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