CN107433201A - A kind of hydrogenation of petroleum resin catalyst and preparation method thereof - Google Patents
A kind of hydrogenation of petroleum resin catalyst and preparation method thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of hydrogenation of petroleum resin catalyst and preparation method thereof, and the present invention is using doping metals Pd, Pt on the basis of pure nickel catalyst, Mo, W or Co, and ultrasound is introduced during co-precipitation, so that the particle diameter of the crystal formed is evenly, it is smaller.The catalyst that the present invention introduces can effectively be catalyzed hydrogenation of petroleum resin reaction, and the Petropols colourity obtained after hydrogenation is shallow, while has higher hydrogenation selectivity, can retain the modified groups such as phenyl ring.
Description
Technical field
The invention belongs to petrochemical industry, more particularly to a kind of hydrogenation of petroleum resin catalyst and preparation method thereof.
Background technology
The Petropols not being hydrogenated with are also known as muntenite, due to unsaturated double strong presence, have light and heat are unstable to lack
Point, process is odorous to shed.And it is that acquisition heat endurance is good to be hydrogenated with, colourity is shallow, the small high-end applications Petropols of taste
Most efficient method.In recent years, Hydrogenation Technology of Petroleum Resin and catalyst have the development advanced by leaps and bounds.Petropols make
Needed during and the polymer complex such as EVA, SIS, and SBS uses, form the important component of adhesive.In oil tree
Introduced in fat and retain phenyl ring isopolarity functional group, the polymer such as Petropols and EVA, SBS can be made to have more preferable compatibility.
Ni catalyst active height in hydrogenation process, cost is low double strong, but many useful polar functional group such as phenyl ring etc.,
It can be hydrogenated simultaneously so that the compatibility poor of resin.Patent CN105013489A, which describes one kind and prepared, is supported on SiO2On
Cu-Ni catalyst method, using hydro-thermal method prepare it is dispersed, have hollow-core construction Cu-Ni/SiO2Catalysis
Agent, this method operating procedure is simple, and purity is high, and the catalyst of preparation has good controllability and feasibility of batch preparation.
A kind of method that patent CN104525207A describes the preparation and its catalysis C5 hydrogenation of saturated hydrogenation Ni catalyst.The patent makes
Use Al2O3For carrier, active component includes the one or more in Ni and K, Na, Co, Cu, Zn, Mo, applied to smart C5 oil tree
Fat is hydrogenated with, and reaction condition is gentle, and hydrogenation efficiency is high.United States Patent (USP) US 5356847,5498587,6524994, describe nickel and urge
The preparation method of agent, and the application in hydrogenation of petroleum resin.Above-mentioned Raney nickel is during hydrogenated petroleum resin, all
The shortcomings that selective poor.Raney nickel is difficult the depth of control hydrogenation in industrial production, it is difficult to retains required functional group
Or the physical property of required resin.For example, aromatic ring modified resin is being hydrogenated with using pure nickel catalyst, while color is eliminated,
It is difficult to accomplish to retain aromatic ring.When colourity, which reaches expected, to be required, general aromatic ring, which is also all hydrogenated, to be saturated.Precious metal palladium and
Platinum, and molybdenum, tungsten etc. have the characteristics of selectivity is good, but are not so good as Ni in catalytic activity, and price is general costly.Cause
This, industrially needs a kind of hydrogenation catalyst for having more preferable selectivity, can effectively remove colourity, while and can enough retains such as
The so useful modification side base of phenyl ring.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of hydrogenation of petroleum resin catalyst and its system
Preparation Method.
The technical purpose of the present invention is achieved by following technical proposals：
A kind of hydrogenation of petroleum resin catalyst and preparation method thereof, is carried out as steps described below：
Step 1, nickel salt is prepared with dissolving and being dispersed in distilled water as the soluble-salt in doping metals source
Into water-soluble night, the soluble-salt as doping metals source is palladium salt, platinum salt, molybdenum salt, tungsten salt or cobalt salt, in aqueous nickel salt
It is (5-100) with the ratio between the concentration of palladium salt, platinum salt, molybdenum salt, tungsten salt or cobalt salt (mol ratio)：1；
Step 2, aqueous sodium carbonate is added dropwise in the nickel salt aqueous solution containing doping metals prepared to step 1, makes gold
Belong to nickel ion and doped metal ion forms co-precipitation；
Step 3, carrier, and continual ultrasonic and stirring are added into the reaction system of step 2, so that step 2 is co-precipitated shape
Into nucleus continued growth and uniform deposition on carrier；
Step 4, carrier will be washed after reacting liquid filtering, is sintered, reduces and is passivated after drying, wherein sintering
Temperature is 380-450 degrees Celsius, is sintered in oxygen atmosphere, to remove organic component impurity, and precipitated metal is formed oxygen
Compound phase, sintering time are 8-24 hours；Reduction temperature is 380-450 degrees Celsius, is reduced in hydrogen atmosphere, so that living
Property metal be reduced, the recovery time be 8-24 hours；Passivation temperature is 30-35 degrees Celsius, and atmosphere is the mixed of nitrogen and oxygen
Gas is closed, oxygen purity is 8-10%, and to form very thin oxide layer, passivation time is 8-24 hours.
Moreover, in step 1, described nickel salt is six water nickel nitrates, it can dissolve and be dispersed in distilled water.
Moreover, in step 1, described palladium salt is palladium bichloride, described platinum salt is platinum chloride, and described molybdenum salt is molybdic acid
Amine, described tungsten salt are wolframic acid amine, and described cobalt salt is cobalt chloride.
Moreover, in step 1, the ratio between nickel salt and concentration of palladium salt, platinum salt, molybdenum salt, tungsten salt or cobalt salt (are rubbed in aqueous
That ratio) it is (10-50)：1.
Moreover, in step 2, the addition of sodium carbonate, so that the pH of the nickel salt aqueous solution added after aqueous sodium carbonate
Value reaches alkalescence and is advisable, such as pH value is 8-10, preferably 9-10.
Moreover, in step 2, select stirring and be added dropwise to aqueous sodium carbonate under ultrasound condition, so that the carbon being added dropwise
Sour sodium is uniformly dispersed, and rate of addition is 5-10ml per minute, and mixing speed is 100-200 turns per minute, and ultrasonic power is
30—50w。
Moreover, in step 3, the carrier is alundum (Al2O3) or silica.
Moreover, in step 3, stirring and ultrasound condition are identical with step 2.
Moreover, in step 4, will be washed after reacting liquid filtering to carrier, drying temperature is 60-80 degrees Celsius, when
Between be 8-12 hours, be crushed to powdered be sintered, reduce and be passivated after drying.
Moreover, in step 4, sintering temperature is 400-420 degrees Celsius, sintering time is 10-14 hours.
Moreover, in step 4, reduction temperature is 380-400 degrees Celsius, the recovery time is 10-14 hours.
Moreover, in step 4, passivation temperature is 30-35 degrees Celsius, passivation time is 10-14 hours.
Application of the above-mentioned hydrogenation of petroleum resin catalyst in hydrogenation of petroleum resin, hydrogenation of petroleum resin catalyst and oil
The mass ratio of resin is (1-5)：50, preferably (1-2)：50, i.e., during hydrogenation of petroleum resin, retained aromatic ring,
To remaining aromatic ring in aromatic ring modified resin hydrogenation process.
Compared with prior art, the beneficial effects of the invention are as follows：
1. the present invention combines Ni high catalytic activity, and the selectivity of other metals, prepare existing good catalysis and live
Property, there is the effective catalyst of suitable selectivity again.
2. the present invention uses adulterates the second metal Pd on the basis of pure nickel catalyst, Pt, Mo, W or Co method, and
Ultrasound is introduced during co-precipitation so that the particle diameter of the crystal of formation is evenly, smaller.
3. the catalyst that the present invention introduces can effectively be catalyzed hydrogenation of petroleum resin reaction, the Petropols obtained after hydrogenation
Colourity is shallow, while has higher hydrogenation selectivity, can retain useful modified group as phenyl ring.
4. a catalyst adaptability is good, in the feed containing impurity such as S, Cl in the case of still keep higher catalysis to live
Property, there is higher industrial application value.
Brief description of the drawings
Fig. 1 is the XRD spectra of the catalyst prepared in the present invention, and wherein curve 1 is comparative example, and curve 2 is embodiment 1.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
It is respectively using the assay method of colourity, softening point and aromatic ring hydrogen content in following examples：
Colourity：Using adding moral sodium (Gardener) colorimetric method ASTM D 1544；
Softening point：Using ring and ball method ASTM E 28；
Aromatic ring hydrogen content：Content of the phenyl ring hydrogen in total hydrogen is determined by H-NMR, wherein being referred to using H-NMR method
An Introduction to Proton Nuclear Magnetic Resonance Spectroscopy By Addison
Adult,1976。
Petropols used in the embodiment of the present invention, with reference to Chinese invention patent " Multicomponent copolymer petroleum resin and its preparation
Method ", Application No. 201210080548.2, the applying date are on March 23rd, 2012, publication number CN 103319659, using heat
The dicyclopentadiene petroleum resin of the phenyl ring modification of poly- method synthesis, after tested its softening point be：103, colourity is:6, aromatic ring hydrogen
Content is 16%.When being added dropwise, rate of addition is 10ml per minute；Be stirred with it is ultrasonic when, mixing speed is every
150 turns of minute, ultrasonic power 30w.
Embodiment 1
First (1) in 1 liter of reaction bulb by 18.42g Na2CO3It is added in 300ML water, is warming up to 60 degree.(2) claim
Six water nickel nitrate 40.5g and 2g palladium bichlorides are taken to dissolve in jointly in the 100ML aqueous solution.By (2) under conditions of stirring and be ultrasonic
Solution, it is added dropwise in (1) reaction bulb, has green precipitate to gradually form.After (2) solution is added dropwise to complete.Added into reaction bulb
3g Al2O3Carrier, continue stirring 30 minutes.Then, filter, wash 3 times.At 80 degree, dry 8 hours.Be sintered after drying,
Reduction and passivation, wherein sintering temperature are 380 degrees Celsius, are sintered in oxygen atmosphere, and sintering time is 24 hours；Reduction temperature
Spend for 380 degrees Celsius, reduced in hydrogen atmosphere, the recovery time is 24 hours；Passivation temperature is 30 degrees Celsius, and atmosphere is nitrogen
The mixed gas of gas and oxygen, oxygen purity 8%, passivation time are 24 hours.
Embodiment 2
First, (1) in 1 liter of reaction bulb by 18.42g Na2CO3It is added in 300ML water, is warming up to 60 degree.(2) claim
Six water nickel nitrate 40.5G and 2G platinum chlorides are taken to dissolve in jointly in the 100ML aqueous solution.By (2) under conditions of stirring and be ultrasonic
Solution, it is added dropwise in (1) reaction bulb, has green precipitate to gradually form.After (2) solution is added dropwise to complete.Added into reaction bulb
3g Al2O3Carrier, continue stirring 30 minutes.Then, filter, wash 3 times.At 60 degree, dry 12 hours.Burnt after drying
Knot, reduction and passivation, wherein sintering temperature are 450 degrees Celsius, are sintered in oxygen atmosphere, and sintering time is 8 hours；Reduction
Temperature is 450 degrees Celsius, is reduced in hydrogen atmosphere, and the recovery time is 8 hours；Passivation temperature is 35 degrees Celsius, and atmosphere is
The mixed gas of nitrogen and oxygen, oxygen purity 10%, passivation time are 8 hours.
Embodiment 3
First, (1) in 1 liter of reaction bulb by 18.42g Na2CO3It is added in 300ML water, is warming up to 60 degree.(2) claim
Six water nickel nitrate 40.5G and 3.5G amine molybdates are taken to dissolve in jointly in the 100ML aqueous solution.Will under conditions of stirring and be ultrasonic
(2) solution, it is added dropwise in (1) reaction bulb, has green precipitate to gradually form.After (2) solution is added dropwise to complete.Add into reaction bulb
Enter 3gAl2O3Carrier, continue stirring 30 minutes.Then, filter, wash 3 times.At 80 degree, dry 10 hours.Burnt after drying
Knot, reduction and passivation, wherein sintering temperature are 400 degrees Celsius, are sintered in oxygen atmosphere, and sintering time is 14 hours；Also
Former temperature is 400 degrees Celsius, is reduced in hydrogen atmosphere, and the recovery time is 10 hours；Passivation temperature is 35 degrees Celsius, atmosphere
For the mixed gas of nitrogen and oxygen, oxygen purity 10%, passivation time is 14 hours.
Embodiment 4
First, (1) in 1 liter of reaction bulb by 18.42g Na2CO3It is added in 300ML water, is warming up to 60 degree.(2) claim
Six water nickel nitrate 40.5G and 3.5G wolframic acid amine are taken to dissolve in jointly in the 100ML aqueous solution.Will under conditions of stirring and be ultrasonic
(2) solution, it is added dropwise in (1) reaction bulb, has green precipitate to gradually form.After (2) solution is added dropwise to complete.Add into reaction bulb
Enter 3g Al2O3Carrier, continue stirring 30 minutes.Then, filter, wash 3 times.At 70 degree, dry 12 hours.Burnt after drying
Knot, reduction and passivation, wherein sintering temperature are 420 degrees Celsius, are sintered in oxygen atmosphere, and sintering time is 10 hours；Also
Former temperature is 380 degrees Celsius, is reduced in hydrogen atmosphere, and the recovery time is 14 hours；Passivation temperature is 30 degrees Celsius, atmosphere
For the mixed gas of nitrogen and oxygen, oxygen purity 8%, passivation time is 10 hours.
Embodiment 5
First, (1) in 1 liter of reaction bulb by 18.42g Na2CO3It is added in 300ML water, is warming up to 60 degree.(2) claim
Six water nickel nitrate 40.5G and 3.5G cobalt chlorides are taken to dissolve in jointly in the 100ML aqueous solution.Will under conditions of stirring and be ultrasonic
(2) solution, it is added dropwise in (1) reaction bulb, has green precipitate to gradually form.After (2) solution is added dropwise to complete.Add into reaction bulb
Enter 3g Al2O3Carrier, continue stirring 30 minutes.Then, filter, wash 3 times.At 80 degree, dry 12 hours.Burnt after drying
Knot, reduction and passivation, wherein sintering temperature are 450 degrees Celsius, are sintered in oxygen atmosphere, and sintering time is 14 hours；Also
Former temperature is 400 degrees Celsius, is reduced in hydrogen atmosphere, and the recovery time is 14 hours；Passivation temperature is 30 degrees Celsius, atmosphere
For the mixed gas of nitrogen and oxygen, oxygen purity 8%, passivation time is 14 hours.
Comparative example
First (1) in 1 liter of reaction bulb by 18.42g Na2CO3It is added in 300ML water, is warming up to 60 degree.(2) claim
Six water nickel nitrate 40.5g and 2g palladium bichlorides are taken to dissolve in jointly in the 100ML aqueous solution.By (2) under conditions of stirring and be ultrasonic
Solution, it is added dropwise in (1) reaction bulb, has green precipitate to gradually form.After (2) solution is added dropwise to complete.Added into reaction bulb
3g Al2O3Carrier, continue stirring 30 minutes.Then, filter, wash 3 times.At 80 degree, dry 8 hours.Be sintered after drying,
Reduction and passivation, wherein sintering temperature are 380 degrees Celsius, are sintered in oxygen atmosphere, and sintering time is 24 hours；Reduction temperature
Spend for 380 degrees Celsius, reduced in hydrogen atmosphere, the recovery time is 24 hours；Passivation temperature is 30 degrees Celsius, and atmosphere is nitrogen
The mixed gas of gas and oxygen, oxygen purity 8%, passivation time are 24 hours.
The embodiment of preparation and comparative example are subjected to XRD signs, as shown in Figure 1, it is known that catalyst prepared by the present invention
The second metal-doped nickel-base catalyst is formed, the particle diameter of the crystal of formation is evenly, smaller.The bicyclic resin for taking phenyl ring to modify
250G, it is dissolved in 250ml saturated fat hydrocarbon solvent, adds in 1L autoclave reaction vessels, be separately added into reactor
The catalyst 5G prepared in embodiment 1-5 and comparative example 1.Reactor is closed, and nitrogen displacement 3 times, logical hydrogen boosts to 5MPa.
Slow heating, controlling reaction temperature at 255 degree, in 6MPa. react 3 hours by pressure.Cooling, terminating reaction, hydrogen is discharged, is gone out
Material.Filter off and remove catalyst.The solution rotating of hydrogenation is evaporated, removes solvent.Determine the colourity of product, softening point, phenyl ring hydrogen
Content, it is as a result as shown in the table.
With the catalyst in embodiment 1-5 in identical reaction temperature and under the conditions of the reaction time, compared with comparative example,
To remaining aromatic ring in aromatic ring modified resin hydrogenation process.
It is adjusted according to the technological parameter that present invention is recorded, can prepares the catalyst of the present invention, and is shown
Basically identical performance, has been effectively retained aromatic ring with embodiment.Exemplary description is done to the present invention above, it should explanation
It is that, in the case where not departing from the core of the present invention, any simple deformation, modification or other skilled in the art can
The equivalent substitution of creative work is not spent to each fall within protection scope of the present invention.
Claims (10)
1. a kind of hydrogenation of petroleum resin catalyst, it is characterised in that carry out as steps described below：
Step 1, nickel salt is configured to water with dissolving and being dispersed in distilled water as the soluble-salt in doping metals source
Molten night, the soluble-salt as doping metals source are palladium salt, platinum salt, molybdenum salt, tungsten salt or cobalt salt, in aqueous nickel salt and palladium
Salt, platinum salt, molybdenum salt, the ratio between the concentration (mol ratio) of tungsten salt or cobalt salt are (5-100)：1；
Step 2, aqueous sodium carbonate is added dropwise in the nickel salt aqueous solution containing doping metals prepared to step 1, makes metallic nickel
Ion and doped metal ion form co-precipitation；
Step 3, carrier, and continual ultrasonic and stirring are added into the reaction system of step 2, so that what step 2 co-precipitation was formed
Nucleus continued growth and uniform deposition are on carrier；
Step 4, carrier will be washed after reacting liquid filtering, is sintered, reduces and is passivated after drying, wherein sintering temperature
For 380-450 degrees Celsius, it is sintered in oxygen atmosphere, to remove organic component impurity, and precipitated metal is formed oxide
Phase, sintering time are 8-24 hours；Reduction temperature is 380-450 degrees Celsius, is reduced in hydrogen atmosphere, so that activity gold
Category is reduced, and the recovery time is 8-24 hours；Passivation temperature is 30-35 degrees Celsius, and atmosphere is the gaseous mixture of nitrogen and oxygen
Body, oxygen purity are 8-10%, and to form very thin oxide layer, passivation time is 8-24 hours.
A kind of 2. hydrogenation of petroleum resin catalyst according to claim 1, it is characterised in that in step 1, described nickel
Salt is six water nickel nitrates；Described palladium salt is palladium bichloride, and described platinum salt is platinum chloride, and described molybdenum salt is amine molybdate, described
Tungsten salt be wolframic acid amine, described cobalt salt is cobalt chloride；Nickel salt and palladium salt, platinum salt, molybdenum salt, tungsten salt or cobalt salt in aqueous
The ratio between concentration (mol ratio) is (10-50)：1.
A kind of 3. hydrogenation of petroleum resin catalyst according to claim 1, it is characterised in that in step 2, sodium carbonate
Addition, so that the pH value of the nickel salt aqueous solution added after aqueous sodium carbonate reaches alkalescence and is advisable, such as pH value is 8-10,
It is preferred that 9-10；Selection is being stirred and is being added dropwise to aqueous sodium carbonate under ultrasound condition, so that the sodium carbonate being added dropwise is uniformly dispersed,
Rate of addition is 5-10ml per minute, and mixing speed is 100-200 turns per minute, and ultrasonic power is 30-50w.
A kind of 4. hydrogenation of petroleum resin catalyst according to claim 1, it is characterised in that in step 3, the carrier
For alundum (Al2O3) or silica；Mixing speed is 100-200 turns per minute, and ultrasonic power is 30-50w.
5. a kind of hydrogenation of petroleum resin catalyst according to claim 1, it is characterised in that in step 4, by reaction solution
Carrier is washed after filtering, drying temperature is 60-80 degrees Celsius, and the time is 8-12 hours, and powder is crushed to after drying
Shape is sintered, reduces and is passivated；Sintering temperature is 400-420 degrees Celsius, and sintering time is 10-14 hours；Reduction temperature
For 380-400 degrees Celsius, the recovery time is 10-14 hours；Passivation temperature is 30-35 degrees Celsius, and passivation time is 10-14
Hour.
6. a kind of preparation method of hydrogenation of petroleum resin catalyst, it is characterised in that carry out as steps described below：
Step 1, nickel salt is configured to water with dissolving and being dispersed in distilled water as the soluble-salt in doping metals source
Molten night, the soluble-salt as doping metals source are palladium salt, platinum salt, molybdenum salt, tungsten salt or cobalt salt, in aqueous nickel salt and palladium
Salt, platinum salt, molybdenum salt, the ratio between the concentration (mol ratio) of tungsten salt or cobalt salt are (5-100)：1；
Step 2, aqueous sodium carbonate is added dropwise in the nickel salt aqueous solution containing doping metals prepared to step 1, makes metallic nickel
Ion and doped metal ion form co-precipitation；
Step 3, carrier, and continual ultrasonic and stirring are added into the reaction system of step 2, so that what step 2 co-precipitation was formed
Nucleus continued growth and uniform deposition are on carrier；
Step 4, carrier will be washed after reacting liquid filtering, is sintered, reduces and is passivated after drying, wherein sintering temperature
For 380-450 degrees Celsius, it is sintered in oxygen atmosphere, to remove organic component impurity, and precipitated metal is formed oxide
Phase, sintering time are 8-24 hours；Reduction temperature is 380-450 degrees Celsius, is reduced in hydrogen atmosphere, so that activity gold
Category is reduced, and the recovery time is 8-24 hours；Passivation temperature is 30-35 degrees Celsius, and atmosphere is the gaseous mixture of nitrogen and oxygen
Body, oxygen purity are 8-10%, and to form very thin oxide layer, passivation time is 8-24 hours.
7. the preparation method of a kind of hydrogenation of petroleum resin catalyst according to claim 6, it is characterised in that in step 1
In, described nickel salt is six water nickel nitrates；Described palladium salt is palladium bichloride, and described platinum salt is platinum chloride, and described molybdenum salt is
Amine molybdate, described tungsten salt are wolframic acid amine, and described cobalt salt is cobalt chloride；In aqueous nickel salt and palladium salt, platinum salt, molybdenum salt,
The ratio between tungsten salt or the concentration of cobalt salt (mol ratio) are (10-50)：1.
8. the preparation method of a kind of hydrogenation of petroleum resin catalyst according to claim 6, it is characterised in that in step 2
In, the addition of sodium carbonate, so that the pH value of the nickel salt aqueous solution added after aqueous sodium carbonate reaches alkalescence and is advisable, such as pH
It is worth for 8-10, preferably 9-10；Selection is being stirred and is being added dropwise to aqueous sodium carbonate under ultrasound condition, so that the sodium carbonate being added dropwise
It is uniformly dispersed, rate of addition is 5-10ml per minute, and mixing speed is 100-200 turns per minute, ultrasonic power is 30-
50w；In step 3, the carrier is alundum (Al2O3) or silica；Mixing speed is 100-200 turns per minute, ultrasound
Power is 30-50w.
9. the preparation method of a kind of hydrogenation of petroleum resin catalyst according to claim 6, it is characterised in that in step 4
In, carrier will be washed after reacting liquid filtering, drying temperature is 60-80 degrees Celsius, and the time is 8-12 hours, after drying
It is crushed to powdered be sintered, reduce and be passivated；Sintering temperature is 400-420 degrees Celsius, and sintering time is 10-14 small
When；Reduction temperature is 380-400 degrees Celsius, and the recovery time is 10-14 hours；Passivation temperature is 30-35 degrees Celsius, passivation
Time is 10-14 hours.
10. application of the hydrogenation of petroleum resin catalyst in hydrogenation of petroleum resin as described in one of claim 1-5, it is special
Sign is that the mass ratio of hydrogenation of petroleum resin catalyst and Petropols is (1-5)：50, preferably (1-2)：50, i.e., in oil
During adding hydrogen into resin, retained aromatic ring, aromatic ring is remained in aromatic ring modified resin hydrogenation process.
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