CN105664968B - A kind of catalyst and preparation method thereof for the reaction of C9 hydrogenation of petroleum resin - Google Patents
A kind of catalyst and preparation method thereof for the reaction of C9 hydrogenation of petroleum resin Download PDFInfo
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- CN105664968B CN105664968B CN201511021981.9A CN201511021981A CN105664968B CN 105664968 B CN105664968 B CN 105664968B CN 201511021981 A CN201511021981 A CN 201511021981A CN 105664968 B CN105664968 B CN 105664968B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- 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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Abstract
The invention discloses a kind of catalyst and preparation method thereof for the reaction of C9 hydrogenation of petroleum resin, it is intended to provide a kind of not only with excellent high active of hydrogenation catalysis, it is also resistant to impurity stability simultaneously, the activity stabilized of catalyst is able to maintain under conditions of high S, Cl content, extend the service life of catalyst, catalyst has been widened to the adaptability of material resin, using catalyst prepared by the present invention, the catalyst for the hydrogenation C 9 petroleum resin that available bromine valency is low, form and aspect are shallow, softening point is high；Technical points, the catalyst include 100 parts by weight compound zirconias-alumina support and 8-20 parts by weight Ni, 0.3-2.0 parts by weight Pt, belong to catalyst technical field.
Description
Technical field
Invention is related to a kind of catalyst for hydrogenation reaction, specifically, being a kind of anti-for C9 hydrogenation of petroleum resin
The catalyst answered, the present invention also relate to the preparation method of the catalyst；Belong to catalyst technical field.
Background technique
C9 Petropols are widely used in adhesive tape, hot melt adhesive, road application material, ink and rubber etc..Unhydrogenation
The C9 Petropols single variety of reduction, product quality is not high, especially the inherences such as oil-soluble, compatibility and antioxidative stabilizer
Quality index is unstable.Carrying out catalytic hydrogenating reduction processing to C9 Petropols can preferably solve the above problems, and produce improving
The application range of product is widened while moral character energy and increases value-added content of product.It is basic to the hydrogenating reduction of Petropols at present
It is external that industrial applications stage level entered to the research of Petropols catalytic hydrogenating reduction based on C5, and domestic industry
Research very understatement is led.
The catalyst of early stage is mostly the nickel catalyst being carried on diatomite or aluminium oxide-diatomite, nickel content 40-
60%, it is lower using temperature, generally at 260 DEG C or so.Hydrogenated products index meets the requirements, problem be mainly thruput and
Catalyst life is limited.
In United States Patent (USP) US2824860, US2911395 and US3040009 and British patent GB1202802, GB1176443
The catalyst used is nickel, reduced nickel, molybdenum sulfide, the catalysis of about 58% nickel of tripolite loading preferably through pre-activate
Agent.The specific surface area of the fresh catalyst is about 140m2/ g, reduced nickel and total weight ratio are 2-20% on catalyst, best
For 7-13%.Before carrying out hydrogenation reaction, the resin of thermal polymerization is first preferably dissolved in saturated hydrocarbon solvent, such as hexamethylene, positive heptan
Alkane carries out hydrogenation reaction 5- then at 200-260 DEG C under preferably 210-230 DEG C, 2.0-12.1MPa, preferably 3.0-9.1MPa
7h, resulting hydrogenated petroleum resin yield 90-95%, saybolt colorimeter value are 25 or so, and softening point is 150-180 DEG C, bromine number
For 1-3g/100g.Unfortunately catalyst life is short and product colour also spy is further improved.
In the flat 4-110304 peace 1-165604 of Japan Patent used catalyst be mainly monometallic nickel, monometallic palladium and
The characteristics of catalyst that platinum and alkali metal element are combined, these catalyst is active high, but they are to miscellaneous in Petropols
Matter is more sensitive, is easy inactivation.
Chinese patent CN200610016260.3 discloses a kind of height for unsaturated vegetable and animals oils hydrogenation and removing double bond
Alkaline sedimentation agent solution is put into reaction kettle and is heated to 60-70 DEG C by the preparation method of Raney nickel, and soluble nickel is added in stirring
Salting liquid is precipitated, and alumina support is added after adding in nickel salt solution, washs after stirring 0.5-1.0 hours, is dry, crushing and roasting
Burn high-nickel catalyst.But the catalyst is since in precipitation process, the precipitating reagent of acid nickel salt solution to alkalinity is molten
It is added in liquid, causes the precipitation process environment in reaction kettle inhomogenous, cause precipitated grain size different, influence the work of nickel
Property horizontal performance, reduce the activity of catalyst, and alumina support is added after precipitating, this process belongs to two kinds of solids
Matter is mixed, and the dispersion of nickel is unfavorable for, and reduces the utilization rate of active metal, and catalyst activity is relatively low.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of catalysis for the reaction of C9 hydrogenation of petroleum resin
Agent and preparation method thereof, catalyst provided in invention not only has excellent high active of hydrogenation catalysis, while being also resistant to miscellaneous
Matter stability is able to maintain the activity stabilized of catalyst under conditions of high S, Cl content, extends the service life of catalyst,
Catalyst is widened to the adaptability of material resin, using catalyst prepared by the present invention, available bromine valency is low, form and aspect
Shallowly, the high hydrogenation C 9 petroleum resin of softening point.
In order to solve the above technical problems, first technical solution provided by the invention is as follows:
A kind of catalyst for the reaction of C9 hydrogenation of petroleum resin, the catalyst include 100 parts by weight compound zirconias-
Alumina support and 8-20 parts by weight Ni, 0.3-2.0 parts by weight Pt.
Further, the above-mentioned catalyst for the reaction of C9 hydrogenation of petroleum resin, the catalyst also include 5-10 weight
Measure part expanding agent.
Further, the above-mentioned catalyst for the reaction of C9 hydrogenation of petroleum resin, the compound zirconia-aluminium oxide
The mass ratio of zirconium oxide and aluminium oxide in carrier are as follows: 10-40:60-90.
Further, the above-mentioned catalyst for the reaction of C9 hydrogenation of petroleum resin, the compound zirconia-aluminium oxide
The mass ratio of zirconium oxide and aluminium oxide in carrier are as follows: 15-30:70-85.
Further, the above-mentioned catalyst for the reaction of C9 hydrogenation of petroleum resin, the expanding agent be odium stearate,
One of methylcellulose, polyethylene glycol and starch or any combination.
Second technical solution provided by the invention is to provide the preparation method of above-mentioned catalyst, under this method successively includes
State step:
1) compound zirconia-alumina support is prepared
By boehmite and deionized water mixed solution A with vigorous stirring, then by ZrOCl2·8H2The water-soluble drop of O
It is added in solution A, adds expanding agent, be uniformly mixed after becoming homogeneous system, be slowly added to ammonium hydroxide, until pH value reaches 7-8,
By mixture aging 3-5 hours at room temperature, and ultrasound 15-25min, obtained solid is washed with deionized, Zhi Daoyong
AgNO3Solution, which detects, does not have Cl in filtrate-1Ion, then with ethanol washing, the dry 10-15h at 110-130 DEG C, then
3-5h is roasted under 500-600 DEG C of air atmosphere can be obtained compound zirconia-alumina support；
2) load active component
Catalyst carrier is immersed in the mixed aqueous solution of nickel nitrate and four ammino platinum nitrates, is done at 110-130 DEG C
Dry 10-15h, then 3-5h is roasted under 500-600 DEG C of air atmosphere, carried out before hydrogenation reaction reduction activation to get.
Compared with prior art, technical solution provided by the invention has following technological merit:
1, compound zirconia prepared by the present invention-alumina support specific surface area 150-220m2/g, pore volume 0.4-
0.7ml/g, wherein the addition of zirconium oxide and expanding agent is advantageous to the formation of secondary pore in roasting process, provides for complex carrier
More high aperture size, is capable of providing more favorable plus hydrogen environment, and the application of two-part reactive component improves high-temperature hydrogenation reaction
Under the conditions of precious metal element crystallite anti-agglutinatting property, provide the longer hydrogenation catalyst service life.
2, hydrogenation catalyst prepared by the present invention has very high catalytic activity in C 9 petroleum resin hydrogenation reaction, produces
For object hydrogenated petroleum resin hydrogenation rate up to 98.5%, product coloration < 1 (Gardner method), bromine valency is less than 2mg/100g.It is especially prominent
, for the catalyst after the C 9 petroleum resin of high sulfur content reacts for a long time, hydrogenation rate still keeps 95% or more, illustrates this
For catalyst compared with other catalyst, Sulfur tolerance is more preferable, and experimental result, which is also shown that the catalyst also, has high chlorine resistance.
Detailed description of the invention
Fig. 1 is that catalyst provided by the invention is carried out continuously 2000 hours hydrogenation reaction stability experiment figures.
Specific embodiment
With reference to embodiment, claim of the invention is described in further detail, but do not constituted pair
Any restrictions of the invention, anyone limited times made within the claims in the present invention protection scope modification, still in this hair
Within bright claims.
Embodiment 1
The preparation of catalyst carrier
It weighs boehmite 500g and 2L deionized water to be vigorously stirred, then by the 0.5mol/L's of 1L volume
ZrOCl2·8H2O aqueous solution is added drop-wise in above-mentioned solution with the speed of 5ml/min, then 20g expanding agent tristearin is added into solution
Sour sodium, solution are uniformly mixed after becoming homogeneous system, are slowly added to ammonium hydroxide, until ph value reaches 7-8, at room temperature by mixture
It is aging 4 hours, then 20 minutes ultrasonic.Obtained solid is washed with deionized, until with AgNO3Solution detects filtrate
In there is no Cl-1Ion, then three times with ethanol washing, then by solid at 120 DEG C dry 12h, roasted under 550 DEG C, air atmosphere
Burning 4h can be obtained compound zirconia-alumina support.
Respectively according to above-mentioned preparation method, carrier 2,3,4,5, carrier composition and table are prepared for using different original powder proportions
Sign such as following table
1 carrier original powder of table, which is matched, when to be characterized
Embodiment 2
The load of active component
1-5 carrier 100g (100ml) in embodiment 1 is weighed respectively, and the Ni (NO of 50ml (0.16gNi/ml) is added3)2Nitric acid
Four ammino platinum nitrate (Pt (NH of nickel aqueous solution and 50ml (0.006gPt/ml)3)4(NO3)2) solution is uniformly mixed, it is dry to be put into vacuum
Dry case carries out vacuum impregnation 12 hours at room temperature, 120 DEG C of dryings, and 500 roastings obtain corresponding A-1, A-2, A-3, A- in 4 hours
4, A-5 catalyst.
Embodiment 3
Catalyst activity evaluation
Mixing C 9 petroleum resin is dissolved in cyclohexane solvent, forms the material solution of concentration 10% (wt), wherein sulphur
Content 300ppm, chlorinity 4375ppm.
Raw material mixing C 9 petroleum resin physical property is as follows:
2 material resin physical property of table
Catalyst prepared by embodiment 2 is packed into fixed bed reaction pipe, and 400 DEG C of reduction 3 are small in atmosphere of hydrogen under normal pressure
When, hydrogenation reaction is carried out after making activation of catalyst.Reaction condition: pressure 8.0Mpa, 200 DEG C of bed temperature, liquid air speed 1.0h-1, hydrogen liquor ratio 400:1, reaction mixture first after alkali cleaning, washing hydrogenated mix products through falling film evaporator remove solvent and its
After by-product, after falling film evaporator removes solvent and its by-product, nine hydrogenated petroleum resin of solid carbon is obtained, carries out physical property detection
Analysis.
3 hydrogenation reaction experimental result of table
Embodiment 4
Using catalyst A-1, input concentration is respectively 20% (wt) and 30% (wt), and other conditions add hydrogen with embodiment 3
Reaction result is as follows:
4 different feeds concentration experiment of table:
Embodiment 5
Catalyst prepared by embodiment 2 is packed into fixed bed reaction pipe, raw material Petropols with embodiment 3 under normal pressure in
It is restored 4 hours for 300 DEG C in atmosphere of hydrogen, carries out hydrogenation reaction after making activation of catalyst.It is as follows to change reaction condition: pressure
12.0Mpa, 300 DEG C of bed temperature, liquid air speed 2.0h-1, hydrogen liquor ratio 800:1, reaction mixture is first through adding after alkali cleaning, washing
Hydrogen mix products after falling film evaporator removes solvent and its by-product, obtain after falling film evaporator removes solvent and its by-product
To nine hydrogenated petroleum resin of solid carbon, physical property detection and analysis are carried out.
5 hydrogenation reaction experimental result of table
Using catalyst A-1, experiment condition such as embodiment 5 is carried out continuously 2000 hours Hydrogenation Experiments, and experimental result is as schemed
1: stability experiment figure.
By following example, making and using for the catalyst in the present invention is described.
Catalyst activity and life assessment method: the C 9 petroleum resin of S content 300ppm, Cl content 4375ppm is molten
Solution forms the material solution of 20-30% (wt) concentration, concentration is weight percentage, in tubular fixed-bed loading in hexamethylene
Catalyst, the reduction activation under temperature programming in atmosphere of hydrogen, material resin solution is passed through in reactor and carries out hydrogenation reaction,
Reaction condition: pressure 8.0-12.0Mpa, 200-300 DEG C of bed temperature, liquid air speed 1.0-6.0h-1, hydrogen liquor ratio 400:1-
800:1 adds hydrogen mix products after falling film evaporator removes solvent and its by-product, obtains nine hydrogenated petroleum resin of carbon, carries out
Physical property tests and analyzes.
Analytical and testing instrument and execution standard:
Softening point: domestic SYD-2806F type softening point apparatus executes standard GB/T2007,6-1989
Bromine valency: U.S.'s METTLER TOLEDO DL58 type titrator executes standard ASTMD1159-93
Color value: U.S.'s HunterLab Colour Quest EX colorimetric analysis instrument executes standard ASTME313
Sulfur content: domestic TS-3000 fluorescence constant sulphur appliance executes standard ASTM D5453
Chlorinity: domestic RPA-200A micro-coulometric titration instrument executes standard Shi Ke institute RIPP64 and adds hydrogen saturation computation side
Method.
Add hydrogen saturation factor:
With the performance of above-mentioned analysis detection metrics evaluation catalyst.
For product hydrogenated petroleum resin hydrogenation rate up to 98.5%, product coloration < 1 (Gardner method), bromine valency is less than 2mg/
100g。
Claims (5)
1. a kind of catalyst for the reaction of C9 hydrogenation of petroleum resin, which is characterized in that the catalyst is multiple comprising 100 parts by weight
Close zirconia-alumina carriers and 8-20 parts by weight Ni, 0.3-2.0 parts by weight Pt, 5-10 parts by weight expanding agent；
The catalyst passes sequentially through following step and is made:
1) compound zirconia-alumina support is prepared
By boehmite and deionized water mixed solution A with vigorous stirring, then by ZrOCl2·8H2O aqueous solution is added drop-wise to
In solution A, expanding agent is added, is uniformly mixed after becoming homogeneous system, is slowly added to ammonium hydroxide, until pH value reaches 7-8, will be mixed
It closes object aging 3-5 hours at room temperature, and ultrasound 15-25min, obtained solid is washed with deionized, until with AgNO3
Solution, which detects, does not have Cl in filtrate-1Ion, then with ethanol washing, the dry 10-15h at 110-130 DEG C, then in 500-600
Roasting 3-5h obtains compound zirconia-alumina support under DEG C air atmosphere；
2) load active component
Catalyst carrier is immersed in the mixed aqueous solution of nickel nitrate and four ammino platinum nitrates, the dry 10- at 110-130 DEG C
15h, then 3-5h is roasted under 500-600 DEG C of air atmosphere, carried out before hydrogenation reaction reduction activation to get.
2. the catalyst according to claim 1 for the reaction of C9 hydrogenation of petroleum resin, which is characterized in that described is compound
The mass ratio of zirconium oxide and aluminium oxide in zirconia-alumina carriers are as follows: 10-40:60-90.
3. the catalyst according to claim 2 for the reaction of C9 hydrogenation of petroleum resin, which is characterized in that described is compound
The mass ratio of zirconium oxide and aluminium oxide in zirconia-alumina carriers are as follows: 15-30:70-85.
4. the catalyst according to claim 1 for the reaction of C9 hydrogenation of petroleum resin, which is characterized in that the reaming
Agent is one of odium stearate, methylcellulose, polyethylene glycol and starch or any combination.
5. the preparation method of the catalyst described in claim 1 for the reaction of C9 hydrogenation of petroleum resin, which is characterized in that according to
It is secondary to include the following steps:
1) compound zirconia-alumina support is prepared
By boehmite and deionized water mixed solution A with vigorous stirring, then by ZrOCl2·8H2O aqueous solution is added drop-wise to
In solution A, expanding agent is added, is uniformly mixed after becoming homogeneous system, is slowly added to ammonium hydroxide, until pH value reaches 7-8, will be mixed
It closes object aging 3-5 hours at room temperature, and ultrasound 15-25min, obtained solid is washed with deionized, until with AgNO3
Solution, which detects, does not have Cl in filtrate-1Ion, then with ethanol washing, the dry 10-15h at 110-130 DEG C, then in 500-600
Roasting 3-5h obtains compound zirconia-alumina support under DEG C air atmosphere；
2) load active component
Catalyst carrier is immersed in the mixed aqueous solution of nickel nitrate and four ammino platinum nitrates, the dry 10- at 110-130 DEG C
15h, then 3-5h is roasted under 500-600 DEG C of air atmosphere, carried out before hydrogenation reaction reduction activation to get.
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| CN109569634B (en) * | 2018-11-24 | 2021-12-17 | 徐敏君 | Hydrogenation method for C-V petroleum resin |
| CN109395738B (en) * | 2018-11-24 | 2021-12-14 | 徐敏君 | Hydrogenation catalyst for carbon five petroleum resin and preparation method thereof |
| CN109395739B (en) * | 2018-11-24 | 2021-12-31 | 杭州牛耳科技有限公司 | Petroleum resin hydrogenation catalyst and preparation method thereof |
| CN110404549A (en) * | 2019-08-26 | 2019-11-05 | 北京化工大学 | A kind of the fining preparation and evaluation method of cold poly- hydrogenation of petroleum resin catalyst |
| CN110665523A (en) * | 2019-09-12 | 2020-01-10 | 明光瑞智电子科技有限公司 | Catalyst for hydrogenation reaction of C9 petroleum resin and preparation method thereof |
| CN111333752B (en) * | 2020-02-28 | 2021-06-08 | 宁波工程学院 | Hydrogenation catalysis method of carbon nine resin |
| CN114516926B (en) * | 2022-03-11 | 2023-11-17 | 广东新华粤石化集团股份公司 | Preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin |
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