CN106914259A - A kind of method of hydrotreating of C 5 petroleum resin - Google Patents
A kind of method of hydrotreating of C 5 petroleum resin Download PDFInfo
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- CN106914259A CN106914259A CN201710158460.0A CN201710158460A CN106914259A CN 106914259 A CN106914259 A CN 106914259A CN 201710158460 A CN201710158460 A CN 201710158460A CN 106914259 A CN106914259 A CN 106914259A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a kind of method of hydrotreating of C 5 petroleum resin, using fixed bed reactors；The catalyst is that activated centre is palladium and the loaded catalyst of nickel phosphide, and its hydrogenation process conditions is：180 270 DEG C of reaction temperature, the 15.0MPa of reaction pressure 6.0, the 7.0h of volume space velocity 0.2‑1.Hydrogenation reaction process conditions are relatively mild, hydrogenated petroleum resin good product performance, and the activity stability of catalyst is good.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of C 5 petroleum resin, more specifically using one kind containing zinc oxide-oxygen
Change the catalyst that aluminium composite material is carrier C 5 petroleum resin hydrogenation, for C 5 petroleum resin hydrogenation reaction.
Background technology
C5 and C9 cuts in cracking of ethylene accessory substance generally can be divided into by the thermoplastic resin of polymerization：Fat
Hydrocarbon resin (C5), aliphatic hydrocarbon-aromatic hydrocarbon resin (C5/C9), aromatic hydrocarbon resin (C9) and dcpd resin (DCPD).Due to
Petropols have good water resistance, resistance to acids and bases, weatherability, light fastness aging, are widely used in paint, coating, glue
The field such as mixture and rubber.At present, domestic petroleum resin is influenceed by raw material composition, and its product is general in light yellow or even reddish brown
Color, photostability is poor, it is impossible to as the raw material of high-end product, limit its application.It is catalyzed by Petropols
Hydrogenation, can make molecule internal double bond and phenyl ring saturation, while removing the halide and sulphur, nitrogen impurity of residual in resin.After hydrogenation
The general white or Transparent color of Petropols, and weatherability, cohesive, photo and thermal stability etc. be significantly improved, and expands
The range of application of Petropols, improves the application added value of Petropols.At present, foreign oil adding hydrogen into resin technology has been
Commercial Application and popularization are obtained, the eighties, the hydrogenation of petroleum resin one of developed countries reaches 6.6 ten thousand tons/year, and it represents skill
Art is the Hydrogenation Technology of Petroleum Resin of U.S. Yi Shiman.With the fast development of China's Petrochemical, ethylene production capacity is notable
Lifting, cracking c5, the quantity of C9 cuts are constantly increasing.This part resource is effectively utilized, causes Domestic Scientific Research personnel's
Pay attention to, and research dynamics is progressively increased in the later stage nineties.Supported nickel catalyst is relatively low due to its cost, obtains larger concern simultaneously
Be widely studied, its carrier mainly has aluminum oxide, magnesia, activated carbon or a various composites, but exploitation catalyst by
In there is a problem of that hydrogenation activity is poor, it is not well used always.
The composite of zinc oxide and aluminum oxide is frequently as the carrier material of catalyst, and application field is extensive.Spinel-type
Composite oxides are the up-and-coming Inorganic Non-metallic Materials of a class, and height is widely used in a series of good characteristics
The fields such as adiabator, catalyst and catalyst carrier.The conventional preparation method of the domestic and international material includes infusion process, mechanical mixture
Method, coprecipitation and peptisation.Wherein, because infusion process and mechanical mixing use alumina material as predecessor, pass through
The specific surface area of alumina material is adjusted, both approaches can prepare the composite of high specific surface area, but due to multiple
Aluminum oxide and zinc oxide interaction in condensation material is weaker, and the loss of zinc oxide is easily produced during use, typically adopts
The two is promoted to form spinelle to avoid the loss of zinc oxide with the method for high-temperature roasting；And coprecipitation and peptisation are used and contained
The compound of aluminum and zinc prepares zinc-aluminium precursor by precipitation or peptization, and aluminum and zinc is stronger by reacting generation in preparation process
Interaction the zinc oxide during use can be avoided to be lost in, but the specific surface area that peptisation prepares material is minimum, makes
It is restricted when it is used as catalysis material.
With activated carbon or silica as carrier, it is active component to use nickel, nickel molybdenum, nickel tungsten to CN201510431240.1, is adopted
Loaded with equi-volume impregnating；CN103386308A discloses a kind of C5 hydrogenation of petroleum resin Raney nickel, with activity
Charcoal loads the auxiliary agents such as Ni, addition Zn, Co and forms non-crystaline amorphous metal nano particle, and reaction conversion ratio and selectivity increase；Patent
CN102935367A discloses a kind of palladium base C5 hydrogenation of petroleum resin catalyst, with aluminum oxide, titanium oxide composite carrier load palladium,
Molybdenum/tungsten active component, the mass fraction of supported palladium is 0.2%-0.4%, and the catalyst has low temperature hydrogenation activity, and good is anti-
Impurity ability and stability, but production cost and expense are larger；Patent CN201510886175.1 discloses a kind of catalysis C5, C9
Hydrogenation of petroleum resin catalyst and its preparation method and application, with nano particle as active component, magnesia is carrier to catalyst,
The features such as nano nickel/the magnesia catalyst of preparation has catalysis activity high, good stability, is easily isolated, in gentle reaction
Under the conditions of Petropols are hydrogenated with, the degree of unsaturation of resin is significantly reduced, form and aspect be improved significantly.
CN201110234152.4, CN201310195238.X use aluminium oxide-titanium oxide double oxide as carrier, and in nickel system
Middle silver-doped, molybdenum, tungsten, cobalt, cerium isoreactivity component.Japan Patent JP3265369 and JP3289326 is urged using Ni diatomite
Agent, and add the elements such as barium, calcium, magnesium, copper to be modified in system.
Subject matter hydrogenation process conditions present in existing C 5 petroleum resin hydrogenation process are harsh, are soft hydrogenation resins
Change point is low, and the anti-impurity ability of hydrogenation catalyst, activity stability are poor.
The content of the invention
The invention provides a kind of method of hydrotreating of C 5 petroleum resin, for the C 5 petroleum resin high-grade stone of hydrogenation production
Oleoresin product.The present invention comprises the following steps：
The Catalyst packing of palladium and nickel phosphide will be loaded with fixed bed reactors, start after airtight experiment is qualified into through
The mixing C 5 petroleum resin raw material of solvent dissolving, hydrogenation reaction is carried out under the reaction process condition of setting, hydrogenated products with
Solvent carries out performance evaluation after separating.
Catalyst of the present invention is that the palladium oxide nickel phosphide being carried on the complex carrier containing zinc oxide-alumina is urged
Agent.
The composition of described catalyst is with oxidation material gauge, including following component：Compound load containing zinc oxide-alumina
Body 78.0-96.0wt%, active component palladium oxide 1.0-8.0wt%, nickel phosphide 1.0-15.0wt%, lanthana 0.1-
2.5wt%；
The preparation method of described catalyst, comprises the following steps：
The soluble-salt of palladium and lanthanum wiring solution-forming, compound load of the dipping containing zinc oxide-alumina together with nickel phosphide will be contained
Body, dries, and roasting obtains the catalyst of C 5 petroleum resin hydrogenation；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, auxiliary agent
Component phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 5.0-
40.0wt%, alumina content is 60.0-95.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area 200-
300m2/g；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, is prepared containing gahnite
Zinc oxide stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid is added
The acid solution containing Sodium Polyacrylate after acidification, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping,
Dried process, calcination process is obtained containing zinc oxide-alumina composite carrier.
Fixed bed reactors of the present invention, are fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably solid
Fixed bed adiabatic reactor.
Described C 5 petroleum resin hydrogenation reaction, its process conditions is：180-270 DEG C of reaction temperature, reaction pressure
6.0-15.0MPa, volume space velocity 0.2-7.0h-1；
190-220 DEG C of preferable reaction temperature, reaction pressure 7.0-10.0MPa, volume sky 1.0-3.0h-1。
The composition of preferred catalyst is with oxidation material gauge, including following component：Compound load containing zinc oxide-alumina
Body 78.0-96.0wt%, active component palladium oxide 1.0-8.0wt%, nickel phosphide 1.0-15.0wt%, lanthana 0.1-
2.5wt%；More preferably contain the complex carrier 80.0-94.0wt%, active component palladium oxide 2.0- of zinc oxide-alumina
6.0wt%, nickel phosphide 3.0-7.0wt%, lanthana 0.5-2.0wt%；
Preferably, the composition of described complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is
10.0-35.0wt%, alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.2-1.2wt%, K2O1.0-2.5wt%, MgO 1.0-2.5wt%, complex carrier specific surface area
200-300m2/g。
Drying of the present invention, roasting obtains the catalyst of C 5 petroleum resin hydrogenation, refers to that 6 are dried at 120 DEG C
Hour, roasting obtains catalyst in 6-8 hours at 450-650 DEG C；Described dried process, calcination process refers to 110-150 DEG C and does
Dry treatment 4-8 hours, calcination process 4.5-8 hours at 550 DEG C -700 DEG C.
The described zinc oxide stratified material prepared containing gahnite, is preferably prepared by the following preparation method：Will
Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and sodium metaaluminate and sodium carbonate are added in a zinc solution
Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Be further continued for be added dropwise another zinc salt it is molten
Liquid；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5
Solution；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc solution whole completion of dropping, finally
Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop
Determine process to be completed in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing dries 4-10h to neutrality at 80-140 DEG C,
450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratified material containing gahnite.
The soluble zinc salt is zinc nitrate or zinc chloride.
The acid solution containing Sodium Polyacrylate after described nitric acid acidification, is preferably prepared by the following preparation method：
Deionized water is heated to 30-90 DEG C, then nitric acid is dissolved into deionized water, add Sodium Polyacrylate, and dissolved
Entirely, the acid solution containing Sodium Polyacrylate is obtained.The addition of described Sodium Polyacrylate is preferably the 0.6- of boehmite
12.0wt%.The Sodium Polyacrylate of acidified treatment, its is uniformly dispersed more preferably, and zinc oxide, alumina powder mixing are more
Uniformly.
The addition of the sesbania powder is preferably the 0.2-7.0wt% of boehmite.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also using potassium and
Magnesium is modified to the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable too high, preferably configuration concentration
Carrier surface is sprayed less than the potassium nitrate and magnesium nitrate aqueous solution when preparing complex carrier, carrier is preferably carried out as follows
Surface is modified：Aqueous solution spray complex carrier containing zinc oxide-alumina of the configuration containing potassium nitrate and magnesium nitrate, through drying, roasting
Burning obtains used additives potassium and magnesium carries out the modified zinc oxide-alumina complex carrier in surface, and control zinc oxide-alumina is compound to be carried
Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 0.2-2.5wt% in body, and aoxidize carrier surface
The content of potassium and magnesia is 1.4-1.6 times of internal oxidation potassium and content of magnesia.
Compared with prior art, the present invention has advantages below：
1st, the method for hydrotreating of C 5 petroleum resin of the present invention, catalyst activity is high, and hydrogenation conditions are gently harsh
Spend low, hydrogenated petroleum resin excellent product performance, long-term operation excellent performance.
2nd, the zinc oxide containing gahnite of the invention is that alternately prepared by titration by non-constant pH, i.e., in non-constant pH
Prepared by the alternating titration of sodium carbonate liquor and zinc-containing solution under the conditions of value, containing aluminium, accordingly, it would be desirable to zinc-containing solution is divided into number
Part, the sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is acid solution, between aluminium zinc solution
Repeatedly alternately titration pH value is swung between soda acid, be conducive to aluminium zinc precursor thing can orderly accumulation be layer structure, through straight
Connect that low-temperature bake can be uniformly dispersed and specific surface area can be in 150-220m2The point containing zinc-aluminium regulated and controled between/g is brilliant
The zinc oxide material of stone, it is to avoid the precursor obtained using alkaline solution one step titration zinc-aluminium mixed solution needs high-temperature roasting
The problem of fixed zinc oxide, decreases hydrothermal treatment process.The material has larger specific surface area.
3rd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate, poly- third in zinc oxide-alumina complex carrier
Olefin(e) acid sodium can be repaired and improve catalytic inner pore passage structure, and diffusion effect is good in catalyst.The carrier is prepared into Petropols
Hydrogenation catalyst, such as hydrogenation catalyst, are conducive to adjusting the acidity of hydrogenation catalyst, and catalytic inner duct knot is improved in finishing
Structure, suppresses catalytic inner coking deactivation, improves the stability of hydrogenation of petroleum resin catalyst.
4th, the present invention obtain containing zinc oxide-alumina composite carrier, after surface is through potassium and magnesium modification, make carrier table
The content of the concentration formation concentration difference of the potassium in face and the concentration of magnesium and carrier inside potassium and magnesium, carrier surface potassium and magnesium is higher than carrier
The molar content or mass content of the content of internal potassium and magnesium, i.e., outside potassium and magnesium can be the 1.4- of the content of internal potassium and magnesium
1.6 times, carrier surface is tended to equally distributed state, reduce the acidity of carrier surface, the carrier can be improved
The specific surface area of catalyst, suppresses catalyst surface carbon deposit inactivation.Improvement to carrier surface should not use dipping method, dipping to carry
Body surface face can make large quantity of moisture enter carrier, and intensity is deteriorated, and does not reach the purpose for improving carrier surface Jie-macropore ratio.Using
The mode of spray is modified to complex carrier surface, is capable of the partial pore on effective peptization complex carrier surface, so favourable
In the micropore ratio for reducing complex carrier surface, complex carrier surface Jie-macropore ratio is improved, promote complex carrier surface to produce
Go out more active sites load centres, effectively improve catalyst activity.
5th, through potassium and magnesium modification, the complex carrier containing zinc oxide-alumina can be made carrier surface of the present invention
To be used for the hydrogenation reaction of C 5 petroleum resin after the carrier loaded active component of C 5 petroleum resin hydrogenation catalyst.
Specific embodiment
A kind of method of hydrotreating of C 5 petroleum resin of the invention is carried out further with comparative example by the following examples
Describe in detail.But these embodiments are not regarded as limiting of the invention.
Prepare primary raw material source used by catalyst：Reagent of the present invention is commercially available prod.
Raw material is cracking of ethylene C5 mixing Petropols, and the resin is by Gardener after desulfurization dechlorination and de- impurity treatment
Colourity is 9, bromine valency 18gBr/100g oil, softening point 119.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, by 0.24kg sodium metaaluminates and 0.30kg sodium carbonate
It is dissolved in 4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature keeps 80
DEG C, mixed solution containing aluminium to pH value is added dropwise thereto and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise
To in hybrid system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；Mixed solution containing aluminium and zinc-containing solution alternately drip
Fixed, until zinc-containing solution is all added, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h.
After 80 DEG C of aging 4h, cooling washing dries 3h to the mixture for arriving to neutrality in 135 DEG C of air atmospheres, in 500 DEG C of roastings
9h, obtains the dispersed zinc oxide stratified material containing gahnite, and in terms of oxide, the content of zinc oxide is 65%；
Specific surface area is 196m2/g。
Weigh phosphatase 11 .04g, potassium nitrate 2.43g respectively, magnesium nitrate 16.88g is dissolved completely in 60g distilled water to be made into and contains
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.By 40g, zinc oxide and 164.3g boehmites ground and mixed containing gahnite are uniform, add 6.0g sesbania powders,
Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are roasted at 580 DEG C
Burn treatment and obtain within 7 hours the complex carrier containing zinc oxide-alumina.Complex carrier specific surface area 276m2/g.Complex carrier includes
Zinc oxide 24.0wt% containing gahnite, aluminum oxide is 70.6wt%, and adjuvant component phosphorus, potassium, content of magnesium are respectively P2O5
0.4wt%, K2O 2.5wt%, MgO 2.5wt%.
5.0g palladium bichlorides are taken, 7.96g nickel phosphides and 1.55g lanthanum nitrates are added in 30ml distilled water, add ammoniacal liquor regulation
PH value dilutes after 3.0, then with deionized water, and wiring solution-forming impregnates the spherical complex carrier 100g containing zinc oxide-alumina, obtains
The catalyst precursor for arriving is calcined 6h after drying 6h at 120 DEG C at 450 DEG C, obtains the catalyst 1 of C 5 petroleum resin hydrogenation.Urge
Agent 1 is mainly constituted：Palladium oxide 3.5wt%, nickel phosphide 3.0wt%, lanthana 0.6wt%, it is compound containing zinc oxide-alumina
Carrier 93.9wt%.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and hydrogenation reaction, hydrogenated products are carried out under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are：190 DEG C of reaction temperature, reaction pressure 10.0MPa, volume is empty
Fast 1.0h-1.Separation mixing C 5 petroleum resin sample is taken after reaction about 55h to be analyzed.Analysis result shows product
Gardener colourities are 0.5, bromine valency 1.84gBr/100g oil, softening point 105.Sampling analysis result table after 500h long-term operations
It is bright：The Gardener colourities of C 5 petroleum resin product are 1, bromine valency 1.2gBr/100g oil, softening point 106.Result shows：Not
The activity stability of the catalyst reaction of surface modification is declined slightly, and overall performance is still good.
Comparative example 1
The zinc nitrate solution of amount same as Example 1, sodium metaaluminate and sodium carbonate liquor are well mixed by blending method, with reality
Apply that the zinc-aluminium mol ratio of example 1 is identical, similarity condition is aging, washing, dry, roasting obtains the oxide material containing zinc-aluminium.Zinc oxide
Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the friendship of aluminum solutions
For titration, zinc-aluminium stratified material can be obtained, under the conditions of two kinds of material zinc-aluminium mol ratio identicals, embodiment 1 is containing zinc-aluminium point
The specific surface area of the zinc oxide stratified material of spar is higher.
Weigh phosphatase 11 .04g, potassium nitrate 2.53g respectively, magnesium nitrate 16.88g is dissolved completely in 60g distilled water to be made into and contains
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.By 40g, oxide material and 164.3g boehmites ground and mixed containing zinc-aluminium are uniform, add 6.0g sesbania powders, gather
PAA acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are calcined at 580 DEG C
Treatment obtains carrier in 7 hours.5.0g palladium bichlorides are taken, 5.31g nickel phosphides and 1.55g lanthanum nitrates are added in 30ml distilled water, plus
Enter ammoniacal liquor regulation pH value to be diluted after 3.0, then with deionized water, wiring solution-forming dipping is spherical compound containing zinc oxide-alumina
Carrier 100g, the catalyst precursor for obtaining is calcined 6h, main composition at 450 DEG C after drying 6h at 120 DEG C：Palladium oxide
3.5wt%, nickel phosphide 2.0wt%, lanthana 0.6wt%, the complex carrier 93.9wt% containing zinc oxide-alumina.Obtain right
Than catalyst 1.
By comparative catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is
The small porcelain balls of φ 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight conjunction
Start after lattice into the C 5 petroleum resin raw material being dissolved by the solvent, and hydrogenation reaction is carried out under certain process conditions, hydrogenation is produced
Product carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are：190 DEG C of reaction temperature, reaction pressure 10.0MPa, volume is empty
Fast 1.0h-1.Separation mixing C 5 petroleum resin sample is taken after reaction about 55h to be analyzed.Analysis result shows product
Gardener colourities are 1.5, bromine valency 3.24gBr/100g oil, softening point 104.
Embodiment 2
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.7.In terms of oxide, the content of zinc oxide is 70%；Specific surface area is 191m2/g。
Complex carrier includes the zinc oxide 32wt% containing gahnite, and aluminum oxide is 67wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.6wt%, K2O 1.0wt%, MgO 1.0wt%.Complex carrier specific surface area 279m2/g。
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration, as maceration extract, weighs nitric acid respectively containing potassium nitrate and magnesium nitrate aqueous solution
Potassium, magnesium nitrate is dissolved completely in 30ml distilled water, then dilutes wiring solution-forming spray zinc oxide-alumina with deionized water
Complex carrier so that the content of carrier outside potassium and magnesium is 1.4 times of the content of internal potassium and magnesium.Used through drying, roasting
Auxiliary agent potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.Complex carrier specific surface area 238m2/g。
Palladium bichloride is taken, nickel phosphide and lanthanum nitrate are added in 30ml distilled water, add ammoniacal liquor to adjust pH value after 3.0, then
Diluted with deionized water, wiring solution-forming impregnates the spherical complex carrier 100g containing zinc oxide-alumina, specific steps are same to implement reality
Example 1, the catalyst precursor for obtaining is calcined 6h after drying 6h at 120 DEG C at 500 DEG C, obtains the catalysis of C 5 petroleum resin hydrogenation
Agent 2.Catalyst 2 is mainly constituted：Palladium oxide 3.5wt%, nickel phosphide 5.0wt%, lanthana 1.0wt%, containing zinc oxide-alumina
Complex carrier 90.5wt%.
By catalyst 2 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and hydrogenation reaction, hydrogenated products are carried out under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are：220 DEG C of reaction temperature, reaction pressure 9.0MPa, volume is empty
Fast 1.2h-1.Separation mixing C 5 petroleum resin sample is taken after reaction about 55h to be analyzed.Analysis result shows product
Gardener colourities are 0, bromine valency 0.82gBr/100g oil, softening point 102.Sampling analysis result table after 500h long-term operations
It is bright：The Gardener colourities of C 5 petroleum resin product are 0.5, bromine valency 1.21gBr/100g oil, softening point 103.Result shows：
The activity stability of the catalyst reaction of surface modification is declined slightly, and overall performance is excellent.
Embodiment 3
The preparation method and step of the complex carrier containing zinc oxide-alumina are with embodiment 1.Prepare containing gahnite
Zinc oxide, pH value is adjusted to 9.3.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 63%；Compare table
Area is 214m2/g。
Complex carrier includes the zinc oxide 18.3wt% containing gahnite, and aluminum oxide is 79wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.9wt%, K2O 2.0wt%, MgO 1.6wt%.Complex carrier specific surface area 242m2/g。
Palladium bichloride is taken, nickel phosphide and lanthanum nitrate are added in 30ml distilled water, add ammoniacal liquor to adjust pH value after 3.0, then
Diluted with deionized water, wiring solution-forming impregnates the spherical complex carrier 100g containing zinc oxide-alumina, specific steps are same to implement reality
Example 1.Catalyst is calcined 6.0h after drying 6h at 120 DEG C at 550 DEG C, obtains hydrogenation catalyst 3.Catalyst 3 is mainly constituted：Oxidation
Palladium 2.5wt%, nickel phosphide 3.5wt%, lanthana 1.5wt%, the complex carrier 92.5wt% containing zinc oxide-alumina.
By catalyst 3 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and hydrogenation reaction, hydrogenated products are carried out under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are：210 DEG C of reaction temperature, reaction pressure 9.0MPa, volume is empty
Fast 0.6h-1.Separation mixing C 5 petroleum resin sample is taken after reaction about 55h to be analyzed.Analysis result shows product
Gardener colourities are 0.5, bromine valency 2.47gBr/100g oil, softening point 104.
Embodiment 4
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.6.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 75%；Compare table
Area is 213m2/g。
Complex carrier includes the zinc oxide 22.9wt% containing gahnite, and aluminum oxide is 75wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O51.1wt%, K2O 1.5wt%, MgO 1.8wt%.Complex carrier specific surface area 256m2/g。
Palladium bichloride is taken, nickel phosphide and lanthanum nitrate are added in 30ml distilled water, add ammoniacal liquor to adjust pH value after 3.0, then
Diluted with deionized water, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, specific steps are with implementation
Example 1.Catalyst is calcined 4.0h after drying 6h at 120 DEG C at 600 DEG C, obtains hydrogenation catalyst 4.Catalyst 4 is mainly constituted：Oxygen
Change palladium 2.5wt%, nickel phosphide 6.0wt%, lanthana 1.0wt%, the complex carrier 90.5wt% containing zinc oxide-alumina.
By catalyst 4 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and hydrogenation reaction, hydrogenated products are carried out under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are：200 DEG C of reaction temperature, reaction pressure 10.0MPa, volume is empty
Fast 0.8h-1.Separation mixing C 5 petroleum resin sample is taken after reaction about 55h to be analyzed.Analysis result shows product
Gardener colourities are 0.0, bromine valency 0.62gBr/100g oil, softening point 100.
Embodiment 5
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.7.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 67%；Compare table
Area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 68wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.6wt%, K2O 1.0wt%, MgO 0.8wt%.Complex carrier specific surface area 279m2/g。
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration is containing potassium nitrate and the compound load of magnesium nitrate aqueous solution spray zinc oxide-alumina
Body so that the content of carrier outside potassium and magnesium is 1.6 times of the content of internal potassium and magnesium.Used additives potassium is obtained through drying, roasting
With the zinc oxide-alumina complex carrier that magnesium carries out surface modification.
Palladium bichloride is taken, nickel phosphide and lanthanum nitrate are added in 30ml distilled water, add ammoniacal liquor to adjust pH value after 3.0, then
Diluted with deionized water, be made into maceration extract and impregnate the spherical complex carrier 100g containing zinc oxide-alumina, specific steps are with implementation
Example 1.Catalyst is calcined 4.0h after drying 6h at 120 DEG C at 600 DEG C, obtains hydrogenation catalyst 5.Catalyst 5 is mainly constituted：Oxygen
Change palladium 5.5wt%, nickel phosphide 6.0wt%, lanthana 1.0wt%, the complex carrier 87.5wt% containing zinc oxide-alumina.
By catalyst 5 and the small porcelain balls 1 of φ 1mm:It is fitted into 100ml fixed bed reactors after 1 mixing, filling order is φ
The small porcelain balls of 1mm, catalyst porcelain ball mixture, the small porcelain balls of φ 1mm, after Catalyst packing is finished, carry out airtight experiment, airtight qualified
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and hydrogenation reaction, hydrogenated products are carried out under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are：190 DEG C of reaction temperature, reaction pressure 9.0MPa, volume is empty
Fast 1.5h-1.Separation mixing C 5 petroleum resin sample is taken after reaction about 55h to be analyzed.Analysis result shows product
Gardener colourities are 0, bromine valency 0.65gBr/100g oil, softening point 98.Sampling analysis result shows after 500h long-term operations：
The Gardener colourities of C 5 petroleum resin product are 0, bromine valency 0.84gBr/100g oil, softening point 100.Result shows：Through table
The catalyst reaction activity of face modification is high, and selectivity is good, and 800h long-term operation activity has no and is decreased obviously, it was demonstrated that the hydrogenation side
Method overall performance is excellent.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of method of hydrotreating of C 5 petroleum resin, it is characterised in that comprise the following steps：
The Catalyst packing of palladium oxide and nickel phosphide will be loaded with fixed bed reactors, start after airtight experiment is qualified into through
The mixing C 5 petroleum resin raw material of solvent dissolving, hydrogenation reaction is carried out under the reaction process condition of setting, hydrogenated products with
Solvent carries out performance evaluation after separating；
Described catalyst active center is palladium oxide and nickel phosphide, and catalyst carrier is the compound load containing zinc oxide-alumina
Body, the composition of catalyst is with oxidation material gauge, including following component：Complex carrier 78.0- containing zinc oxide-alumina
96.0wt%, active component palladium oxide 1.0-8.0wt%, nickel phosphide 1.0-15.0wt%, lanthana 0.1-2.5wt%；
The preparation method of described catalyst, comprises the following steps：
Soluble-salt containing palladium, nickel phosphide and lanthanum is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried,
Roasting obtains the catalyst of C 5 petroleum resin hydrogenation；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, adjuvant component
Phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 5.0-
40.0wt%, alumina content is 60.0-95.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area 200-
300m2/g；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the oxygen containing gahnite is prepared
Change zinc stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid acidifying is added
The acid solution containing Sodium Polyacrylate after treatment, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, dry
Treatment, calcination process is obtained containing zinc oxide-alumina composite carrier.
2. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：Described fixed bed is anti-
Device is answered, is fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably fixed bed adiabatic reactor.
3. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：Described light dydrocarbon oil
Adding hydrogen into resin reacts, and its process conditions is：180-270 DEG C of reaction temperature, reaction pressure 6.0-15.0MPa, volume space velocity 0.2-
7.0h-1。
4. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 3, it is characterised in that：Described light dydrocarbon oil
Adding hydrogen into resin reacts, and its process conditions is：190-220 DEG C of reaction temperature, reaction pressure 7.0-10.0MPa, volume sky 1.0-
3.0h-1。
5. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：
Described catalyst, including following component：Complex carrier 80.0-94.0wt% containing zinc oxide-alumina, active component
Palladium oxide 2.0-6.0wt%, nickel phosphide 3.0-7.0wt%, lanthana 0.5-2.0wt%；
Described complex carrier, constitutes with oxidation material gauge：Zinc oxide content containing gahnite is 10.0-
35.0wt%, alumina content is 65.0-90.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O 1.0-2.5wt%, MgO 1.0-2.5wt%, complex carrier specific surface area 200-
300m2/g。
6. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：Described preparing contains
The zinc oxide stratified material of gahnite, is to be prepared by the following preparation method：Soluble Zn salting liquid is divided into 2-4 parts,
Under the conditions of 40-80 DEG C, the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate is added in a zinc solution, when pH value reaches
Stop that mixed solution containing aluminium is added dropwise during 8.5-9.5；It is further continued for that another zinc solution is added dropwise；After zinc solution is dripped, continue
Mixed solution containing aluminium is added dropwise, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；To contain aluminium according to the above method to mix
Solution replaces titration with zinc solution, until zinc solution whole completion of dropping, last time dropwise addition mixed solution containing aluminium, work as pH
When value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, and control titration process is completed in 1-6h；In 80-95
After DEG C aging 2-8h, cooling washing dries 4-10h, 450-550 DEG C of roasting 4-10h at 80-140 DEG C to neutrality, is uniformly divided
The scattered zinc oxide stratified material containing gahnite；The soluble zinc salt is zinc nitrate or zinc chloride.
7. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：Described nitric acid acidifying
The acid solution containing Sodium Polyacrylate after treatment, is to be prepared by the following preparation method：Deionized water is heated to 30-90 DEG C,
Then nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and dissolve complete, obtain sour molten containing Sodium Polyacrylate
Liquid.
8. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：Described polyacrylic acid
The addition of sodium is the 0.6-12wt% of boehmite；The addition of the sesbania powder is the 0.2-7wt% of boehmite.
9. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：Described drying, roasting
Burning obtains the catalyst of C 5 petroleum resin hydrogenation, refers to be dried 6 hours at 120 DEG C, is calcined 6-8 hours at 450-650 DEG C
Obtain catalyst；Described dried process, calcination process, be 110-150 DEG C dried process 4-8 hours, at 550 DEG C -700 DEG C roast
Burn treatment 4.5-8 hours.
10. the method for hydrotreating of a kind of C 5 petroleum resin according to claim 1, it is characterised in that：It is described containing oxidation
The complex carrier of zinc-aluminum oxide, carries out surface modification, by such as using potassium and magnesium to the complex carrier containing zinc oxide-alumina
Lower step carries out surface modification：Aqueous solution spray complex carrier containing zinc oxide-alumina of the configuration containing potassium nitrate and magnesium nitrate,
Obtaining used additives potassium and magnesium through drying, roasting carries out the zinc oxide-alumina complex carrier of surface modification, controls zinc oxide-oxygen
Change in aluminium complex carrier potassium oxide and content of magnesia respectively in the range of 0.2-2.0wt% and 0.2-2.0wt%, and make load
The content of body surface face potassium oxide and magnesia is 1.4-1.6 times of internal oxidation potassium and content of magnesia.
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