CN104525198B - A kind of for hydrogenation catalyst preparing hydrogenated petroleum resin and preparation method thereof - Google Patents
A kind of for hydrogenation catalyst preparing hydrogenated petroleum resin and preparation method thereof Download PDFInfo
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- CN104525198B CN104525198B CN201410705478.4A CN201410705478A CN104525198B CN 104525198 B CN104525198 B CN 104525198B CN 201410705478 A CN201410705478 A CN 201410705478A CN 104525198 B CN104525198 B CN 104525198B
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Abstract
The present invention relates to a kind of for hydrogenation catalyst preparing hydrogenated petroleum resin and preparation method thereof, hydrogenation catalyst is Pd/Ag/ the Vth B race metal/γ Al2O3Composite catalyst.Preparation: preparation palladium salt, silver salt, the Vth B race metallic compound are dissolved in solvent, obtain mixed solution；By carrier γ Al2O3It is placed in fluidized-bed reactor, then mixed solution is uniformly sprayed on carrier, obtains complex carrier, dry, roasting, reduction, to obtain final product.The catalyst of the present invention has in preparing hydrogenated petroleum resin and is catalyzed more by force activity, and has the impurity toxicity such as preferable sulfur resistive, nitrogen, halogen, has longer catalyst life.
Description
Technical field
The invention belongs to hydrogenation catalyst and preparation field thereof, urge particularly to a kind of hydrogenation for preparing hydrogenated petroleum resin
Agent and preparation method thereof.
Background technology
Petropols are with the accessory substance C5/C9 cut of ethylene unit as primary raw material, through consolidating that hot polymerization or catalytic polymerization obtain
The middle low phase of state or viscous liquid is to polydispersity polymer.The monomer constituted by resin and molecular structure, can be roughly divided into virtue
Hydrocarbon Petropols, aliphatic petroleum resin and alicyclic petroleum resin etc..It is a large amount of unsaturated owing to Petropols molecule containing
Key and unsaturated cyclic structure, the most all can present certain color, and the gardner color number of resin is generally 3～18#.Meanwhile,
Owing to these unsaturated groups exist, there is shortcoming in Petropols in smell, weatherability, heat endurance, limits it
Range of application.In order to obtain high-quality Petropols applied widely, abroad just have started to oil from 20 century 70s
The hydrogenation modification research of resin.Main purpose is to eliminate the residual double bonds in Petropols molecule and aromatic ring double bond, reduces
Form and aspect, improve compatibility, weatherability etc..
Patent US, 6755963, US, refer to Petropols under the solid catalyst effect carrying nickel in 4952639 and urge
Change hydrogenation technique.Patent US, 6162350 disclose and carry out resin catalysis for catalyst add with VIII race and VI B race metallic compound
The method of hydrogen.Patent US4,384,080 and US4,952,639 describe and make with noble metals such as nickel, palladium, platinum, rhenium, rutheniums
The hydrogenation of petroleum resin method of hydrogenation catalyst, general employing single component metal is catalyst activity component.Patent
US4,540,480 describe a kind of hydrogenation of petroleum resin method, and the active component of used catalyst is the above-mentioned noble metal of combination,
Catalyst carrier typically uses Al2O3, it is said that there is higher active and longer service life, obtain hydrogenated petroleum resin
Iodine number≤60g/100g, gardner color number≤1.
Patent CN200510124213.6, CN200510080028.1 provide a kind of catalysis preparing C 5 hydrogenated petroleum resin
Agent, its catalyst activity component precious metal palladium, transition metal, rare earth metal and the IVth major element, carrier is Al2O3,
Produce for the C5 fraction higher with isoprene, the arene content C 5 hydrogenated petroleum resin as raw material.Patent
CN200910070899.3 describes a kind of catalyst being applicable to C 5 petroleum resin hydrogenation reaction, and this catalyst uses hydrogen-oxygen
Change aluminium, diatomite, expanding agent and rare-earth element modified Al2O3Make carrier, select two in precious metals pd, Ru, Rh
Plant as active component, use rare earth metal to carry out being catalyzed activity allotment simultaneously.Patent CN02137114.8 describes one
By Pd and Pt as hydrogenation active component, carrier is γ-Al2O3Be particularly well-suited to be hydrogenated with dcpd resin and prepare
Hydrogenation catalyst.Patent CN201110327835.4 provides a kind of NiZn/SiO prepared with coprecipitation2Catalyst is used for hydrogen
Change dcpd resin to prepare.It is load that patent CN201110234140.1 provides a kind of Metal Palladium with metal molybdenum or tungsten
Active component, and use the C5 hydrogenation of petroleum resin catalyst of Alumina-titanium oxide composite carrier.Patent
CN201110274726.0 disclose a kind of carrier be the one in aluminum oxide, silica and/or amorphous silicon aluminium oxide or
Several, metal active constituent is two or more the C 9 petroleum resin hydrogenation in transition metals cobalt, aluminium, nickel, tungsten, zinc
Pretreatment catalyst.Patent CN201310316203.7 provides a kind of active component to be precious metals pd, and auxiliary agent is K2O、TiO2,
Carrier is Al2O3Adding hydrogen into resin catalyst.Patent CN201310321131.5 discloses a kind of C5 hydrogenation of petroleum resin and uses
Raney nickel, this catalyst is by absorbent charcoal carrier, and the Ni nano particle being attached on absorbent charcoal carrier, and is attached to
Ni on absorbent charcoal carrier and the non-crystaline amorphous metal nano particle composition of metal promoter, effectively extend C5 hydrogenation of petroleum resin and urge
The service life of agent.
China starts late in the research of hydrogenation of petroleum resin catalyst, and current domestic petroleum adding hydrogen into resin device all uses import
Palladium series catalyst, domestic disclosed adding hydrogen into resin catalyst is showed no industrialization report.And due to the molecular weight of Petropols own
Low, structure is complicated, the impurity content such as sulphur, nitrogen, halogen, colloid is high and more difficult removing, it requires that its hydrogenation catalyst has
There is the antitoxin performance of resistant to sulfur, halogen etc. that preferably catalysis is active and certain.
Summary of the invention
The technical problem to be solved is to provide a kind of hydrogenation catalyst for preparing hydrogenated petroleum resin and system thereof
Preparation Method, this catalyst, with precious metals ag as co-catalyst, contributes to Pd catalyst being uniformly distributed on carrier, increases
Concerted catalysis effect, carries high catalytic activity；Be simultaneously introduced the Vth B race metal, be conducive to suppression Petropols in Determination of Trace Sulfur,
The catalyst poisoning that nitrogen, halogen impurities cause, thus extend catalyst service life.
A kind of hydrogenation catalyst for preparing hydrogenated petroleum resin of the present invention, hydrogenation catalyst is Pd/Ag/ the Vth B race gold
Genus/γ-Al2O3Composite catalyst；By weight percentage, major catalyst Pd, content is 0.5～2.0wt%；Co-catalyst
Ag, content is 0.3～1.5wt%；Co-catalyst the Vth B race metal, content is 0.3～1.5wt%；Catalyst carrier γ
-Al2O3For surplus；Wherein major catalyst Pd, co-catalyst Ag, co-catalyst the Vth B race metal are active component.
The content of described major catalyst Pd is 0.5～1.0wt%, and co-catalyst Ag content is 0.3～0.8wt%.
Described co-catalyst the Vth B race metal is niobium Nb, any one in tantalum Ta, vanadium V, and content is 0.3～0.8wt%.
Described co-catalyst the Vth B race metal is niobium Nb.
Described catalyst carrier γ-Al2O3, specific surface area is 70～120m2/ g, pore volume 0.35～0.45ml/g, bulk density 0.6～
0.7g/cm3。
A kind of preparation method of the hydrogenation catalyst for preparing hydrogenated petroleum resin of the present invention, including:
(1) major catalyst Pd, co-catalyst Ag, the percentage by weight of co-catalyst the Vth B race metal are pressed, preparation palladium salt,
Silver salt, the Vth B race metallic compound are dissolved in solvent, obtain mixed solution；
(2) by carrier γ-Al2O3It is placed in the fluidized-bed reactor that temperature is 110-150 DEG C, then by uniform for above-mentioned mixed solution
It is sprayed in reactor be on the carrier granular of fluidized state, obtains complex carrier, dry removing residual moisture,
Roasting, obtains the catalyst precursor of carrying active ingredients, reduction, obtains for preparing adding of hydrogenated petroleum resin
Hydrogen catalyst.
Palladium salt in described step (1) is the one in palladium nitrate, palladium bichloride, palladium sulfate, carbonate palladium；Silver salt be silver nitrate,
One in silver sulfate, silver chlorate；Vth B race metallic compound is the Vth B race metal chloride, the Vth B race metal oxygen
One in compound, the Vth B race metal boride, the Vth B race metal carbonate.
In described step (1), solvent is hydrochloric acid, nitric acid or sulfuric acid.
In described step (2), sintering temperature is 300-800 DEG C, and roasting time is 2-4h.
Described step (2) is reduced under hydro condition at a temperature of 250-400 DEG C reduce 3h.
Beneficial effect
(1) hydrogenation catalyst disclosed by the invention is on the basis of conventional hydrogenation catalyst precious metal palladium makees active component, passes through
Use silver as co-catalyst, improve Metal Palladium at carrier γ-Al2O3On dispersion effect, and strengthen
The electron-withdrawing power of central metal palladium part, improves activity of hydrocatalyst；
(2) at the Vth B race metal such as niobium, the tantalum etc. that supported on carriers is appropriate so that it is hydrogenation of petroleum resin react in
The trace impurity of residual combines, thus slows down the poisoning of main active component Metal Palladium, improves catalyst life.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1-6
By weight percentage, major catalyst Pd, content is 0.5wt%；Co-catalyst Ag, content is 0.3wt%；Help and urge
Agent the Vth B race metal Nb, content is 0.3wt%；Catalyst carrier γ-Al2O3For surplus；Catalyst carrier γ-Al2O3,
Its specific surface area 110m2/ g, pore volume 0.45ml/g, bulk density 0.65g/cm3。
Preparation method: preparation palladium nitrate, silver nitrate, the Vth B race metal columbium pentachloride are dissolved in hydrochloric acid, obtain mixed solution；
By carrier γ-Al2O3It is placed in the fluidized-bed reactor that temperature is 110 DEG C, then above-mentioned mixed solution is uniformly sprayed
To carrier, obtain complex carrier, be dried, 250 DEG C of roasting 3h, under hydro condition at a temperature of 250 DEG C reduce 3h,
Obtain hydrogenation catalyst.
The parameter of embodiment 2-6 is shown in Table 1, and preparation method is with embodiment 1.
Catalyst performance evaluation: by initial gardner color 5#, softening point 100 DEG C treat hydrogenated petroleum resin in mass ratio 1:
(1～10) are dissolved in boiling range and make at 200～240 DEG C be hydrocracked in aviation kerosine, the catalyst prepared in each embodiment
Hydrogenation reaction, hydrogenation temperature 240～300 DEG C, pressure 8.0～15.0MPa, hydrogen-oil ratio 500: 1, liquid space-time is carried out under with
Speed (LHSV) is 2～4h-1.Resin liquid after hydrogenation reduces pressure under vacuum is at-0.09MPa and distills to 230 DEG C, removing
I.e. obtain hydrogenated petroleum resin after solvent and oligomer, it is carried out as follows detection and analyzes, evaluate catalyst performance.
Analysis and detecting instrument and the standard of execution
Look number: HunterLab UltraScan PRO colour photometer, performs standard ASTM E313
Softening point: Anton Paar RKA5 softening point apparatus, GB/T 2294-1997
Bromine valency: perform standard SH/T 0236-1992.
Hydrogenation catalyst performance is shown in Table 2.
Catalyst component in table 1 embodiment
Table 2 hydrogenation catalyst performance evaluation
Claims (10)
1. the hydrogenation catalyst being used for preparing hydrogenated petroleum resin, it is characterised in that: hydrogenation catalyst is Pd/Ag/ the Vth B race gold
Genus/γ-Al2O3Composite catalyst；By weight percentage, major catalyst Pd, content is 0.5～2.0wt%；Co-catalyst
Ag, content is 0.3～1.5wt%；Co-catalyst the Vth B race metal, content is 0.3～1.5wt%；Catalyst carrier γ
-Al2O3For surplus；Wherein co-catalyst the Vth B race metal be niobium Nb, any one in tantalum Ta, vanadium V.
A kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 1, it is characterised in that sponsor described in:
The content of agent Pd is 0.5～1.0wt%, and co-catalyst Ag content is 0.3～0.8wt%.
A kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 1, it is characterised in that help described in: and urge
Agent the Vth B race tenor is 0.3～0.8wt%.
A kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 1, it is characterised in that help described in: and urge
Agent the Vth B race metal is niobium Nb.
A kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 1, it is characterised in that: described catalysis
Agent carrier γ-Al2O3, specific surface area is 70～120m2/ g, pore volume 0.35～0.45ml/g, bulk density 0.6～0.7g/cm3。
6. a preparation method for the hydrogenation catalyst for preparing hydrogenated petroleum resin as described in claim 1-5 is arbitrary, including:
(1) preparation palladium salt, silver salt, the Vth B race metallic compound are dissolved in solvent, obtain mixed solution；
(2) by carrier γ-Al2O3It is placed in the fluidized-bed reactor that temperature is 110-150 DEG C, then above-mentioned mixed solution is uniformly sprayed
Spill to carrier, obtain complex carrier, dry, roasting, reduction, obtain the hydrogenation for preparing hydrogenated petroleum resin
Catalyst.
The preparation method of a kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 6, its feature exists
In: the palladium salt in described step (1) is the one in palladium nitrate, palladium bichloride, palladium sulfate, carbonate palladium；Silver salt is nitric acid
One in silver, silver sulfate, silver chlorate；Vth B race metallic compound is the Vth B race metal chloride, the Vth B race gold
Belong to the one in oxide, the Vth B race metal boride, the Vth B race metal carbonate.
The preparation method of a kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 6, its feature exists
In: in described step (1), solvent is hydrochloric acid, nitric acid or sulfuric acid.
The preparation method of a kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 6, its feature exists
In: in described step (2), sintering temperature is 300-800 DEG C, and roasting time is 2-4h.
The preparation method of a kind of hydrogenation catalyst for preparing hydrogenated petroleum resin the most according to claim 6, its feature exists
In: under described step (2) is reduced at hydro condition at a temperature of 250-400 DEG C reduce 3h.
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| CN102814184A (en) * | 2012-09-12 | 2012-12-12 | 西北化工研究院 | Catalyst for preparing ethylene glycol by hydrogenating oxalate and preparation method thereof |
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Address after: 315800 Ningbo, Zhejiang Province, new road, Beilun District No. 1069 Co-patentee after: HENGHE MATERIALS & SCIENCE TECHNOLOGY CO., LTD. Patentee after: Ningbo Polytechnic College Address before: 315800 Ningbo, Zhejiang Province, new road, Beilun District No. 1069 Co-patentee before: Zhejiang Henghe Petrochemical Co.,Ltd. Patentee before: Ningbo Polytechnic College |
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Effective date of registration: 20211220 Address after: 315200 no.3511, yuejintang Road, Shupu Town, Zhenhai District, Ningbo City, Zhejiang Province Patentee after: HENGHE MATERIALS & SCIENCE TECHNOLOGY Co.,Ltd. Address before: 315800 No. 1069 Xinda Road, Beilun District, Ningbo City, Zhejiang Province Patentee before: Ningbo Polytechnic Patentee before: Henghe Material Technology Co., Ltd |
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