CN107082847A - A kind of method of hydrotreating of Petropols - Google Patents
A kind of method of hydrotreating of Petropols Download PDFInfo
- Publication number
- CN107082847A CN107082847A CN201710408951.6A CN201710408951A CN107082847A CN 107082847 A CN107082847 A CN 107082847A CN 201710408951 A CN201710408951 A CN 201710408951A CN 107082847 A CN107082847 A CN 107082847A
- Authority
- CN
- China
- Prior art keywords
- alumina support
- catalyst
- hydrotreating
- macroporous structure
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method of hydrotreating of Petropols, using fixed bed reactors；The catalyst is that activated centre is palladium and the loaded catalyst of nickel phosphide, and carrier is the alumina support with macroporous structure, and carrier uses chitosan as expanding agent.Hydrogenation process conditions are：180 270 DEG C of reaction temperature, the 15.0MPa of reaction pressure 6.0, hydrogen to oil volume ratio 100 400, 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 Petropols, more specifically there is macroporous structure aluminum oxide using a kind of
For the hydrogenation of petroleum resin catalyst of carrier, reacted for hydrogenation of petroleum resin.
Background technology
Thermoplastic resin of the C5 and C9 cuts Jing Guo polymerization in cracking of ethylene accessory substance, generally can be divided into：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 constituted by raw material and influenceed, 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.By being catalyzed to 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 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 U.S. Yi Shiman Hydrogenation Technology of Petroleum Resin.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 the problem of 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 be 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, is typically to adopt
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.
CN201510431240.1 uses nickel, nickel molybdenum, nickel tungsten for active component, adopted using activated carbon or silica as carrier
Loaded with equi-volume impregnating；CN103386308A discloses a kind of C5 hydrogenation of petroleum resin Raney nickel, with activity
Charcoal loads Ni, adds the auxiliary agents such as Zn, Co formation 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, catalyst is using nano particle as active component, and magnesia is carrier,
The features such as nano nickel/magnesia catalyst of preparation has that catalytic activity is high, stability is good, 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 are urged using Ni diatomite
Agent, and the element such as addition barium, calcium, magnesium, copper is modified in system.
Subject matter hydrogenation process conditions present in existing hydrogenation of petroleum resin process are harsh, are hydrogenation resin softening points
Low, 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 Petropols, high-grade Petropols production is produced for hydrogenation of petroleum resin
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, carries out hydrogenation reaction under the reaction process condition of setting, hydrogenated products with
Performance evaluation is carried out after solvent separation.
Catalyst of the present invention is to be carried on palladium oxide and nickel phosphide on the alumina support with macroporous structure to urge
Agent.Composition is composed of the following components with oxidation material gauge：Alumina support 75.0-96.0wt% with macroporous structure,
Active component palladium oxide 1.0-10.0wt%, nickel phosphide 3.0-15.0wt%；
It is preferred that, the alumina support with macroporous structure accounts for 83.0-94.5wt%, active component palladium oxide 2.5-
9.0wt%, nickel phosphide 4.0-12.0wt%.
Described hydrogenation of petroleum resin method for preparing catalyst, comprises the following steps：
By the soluble-salt containing palladium together with nickel phosphide wiring solution-forming, dipping with macroporous structure alumina support,
Roasting obtains the catalyst of hydrogenation of petroleum resin for 6-8 hours at being dried 6 hours, 450-650 DEG C at 120 DEG C.
Fixed bed reactors of the present invention, are fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably solid
Fixed bed isothermal reactor.
Described hydrogenation of petroleum resin reacts, and its process conditions is：180-270 DEG C of reaction temperature, reaction pressure 6.0-
15.0MPa, hydrogen to oil volume ratio 100-400, volume space velocity 0.2-7.0h-1；
190-220 DEG C of preferable reaction temperature, reaction pressure 7.0-10.0MPa, hydrogen to oil volume ratio 150-350, volume is empty
1.0-3.0h-1。
Alumina support of the present invention with macroporous structure, using chitosan as expanding agent, synthesizes with big
The alumina support of pore structure.
Contain adjuvant component phosphorus and potassium, adjuvant component phosphorus and potassium in the alumina support with macroporous structure, carrier
Content account for the percentage composition respectively P of carrier quality2O50.1-2.5wt%, K2O0.1-2.5wt%, pore-size distribution 60-
180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, preferably pore volume 0.8-2.0ml/g, 0.8-1.3ml/g
Or preferably 1.6-2.0ml/g, specific surface area 250-300m2/ g, carrier uses chitosan as expanding agent.
The alumina support with macroporous structure, aperture can be by changing the addition and expanding agent of expanding agent
Molecular size range be adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm,
The scopes such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, 35-50%, the scope such as 55-75%.
The preparation method of the alumina support with macroporous structure, comprises the following steps：First, it is acidified with acid solution
Boehmite and sesbania powder, are then added in kneader and are well mixed by chitosan, add the mixed of phosphoric acid and potassium nitrate
Solution is closed, finally the acid solution of chitosan-containing is added in boehmite powder and mediates uniform, the acid solution containing expanding agent
Addition be boehmite 0.1-8wt%, preferably 0.2-5.0wt%, by extrusion-shaping-drying-roasting, obtain
Alumina support with macroporous structure.
The process of the acid solution acidified chitosan is as follows：First by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise afterwards, until chitosan dissolving is complete, the acid solution containing expanding agent is obtained.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The addition of acid is advisable with that can be completely dissolved chitosan.Also may be used
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.More than ultrasonic oscillation 10min, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Ripple shakes or magnetic agitation, and expanding agent good dispersion, alumina support is more prone to macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.
The addition of the sesbania powder is the 0.1-7wt% of boehmite.
Mediate or extrusion technique is that the acid solution containing expanding agent configured is added in sesbania powder and boehmite
Well mixed, extrusion, shaping afterwards is dried 3-9 hours, 650-800 DEG C is calcined 4-8 hours, finally gives by 100-160 DEG C
Alumina support with macroporous structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure,
Also contain meso-hole structure simultaneously, macropore range is in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%, be it is a kind of containing being situated between-it is big
The alumina support in hole, and the not homogeneous aperture structure in aperture.
The alumina support with macroporous structure obtained using above-mentioned preparation method, can also be using phosphorus and potassium to carrier
Surface is modified, and the concentration of phosphorus and potassium is unsuitable too high, and preferably configuration concentration is less than phosphoric acid and potassium nitrate when preparing carrier
The aqueous solution sprays carrier surface, and carrier surface modification is preferably carried out as follows：Configure the water-soluble of phosphoric acid and potassium nitrate
Alumina support of the liquid spray with macroporous structure, obtains used additives phosphorus through drying, roasting and potassium carries out the oxidation of surface modification
P in alumina supporter, alumina support of the control with macroporous structure2O5And K2O content is respectively in 0.1-2.5wt% and 0.1-
In the range of 2.5wt%, and carrier surface P2O5 and K2O content is set to be 1.1-1.5 times of internal P2O5 and K2O contents.
Compared with prior art, the present invention has advantages below：
1st, alumina support of the present invention is using chitosan as expanding agent, and expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is adapted to industrialized production.The obtained alumina support with macroporous structure, pore size can adjust, and macropore ratio can
Effectively to control.And carrier is also containing mesoporous, is a kind of Jie-macropore alumina supporter.
2nd, the present invention can also introduce phosphorus and potassium in alumina support, the obtained carrying alumina with macroporous structure
Body, the carrier is prepared into hydrogenation of petroleum resin catalyst, with more preferable adding hydrogen into resin activity, selectivity and stability.
3rd, the alumina support with macroporous structure that the present invention is obtained, using phosphorus and potassium to the oxidation with macroporous structure
Alumina supporter surface is modified, and makes carrier surface P2O5And K2O content is internal P2O5And K21.1-1.5 times of O content.Adopt
Carrier surface is modified with the mode of spray, is capable of the partial pore of effective peptization carrier surface, so advantageously reduces
The micropore ratio of carrier surface, improves carrier surface Jie-macropore ratio, promotes carrier surface to produce more active sites loads
Center, effectively improves catalyst hydrogenation activity.Improvement to carrier surface should not use dipping method, and impregnated carrier surface can make greatly
Amount moisture enters carrier, and intensity is deteriorated, and does not reach the purpose for improving carrier surface Jie-macropore ratio.
4th, the hydrogenation of petroleum resin catalyst carrier that the present invention is provided is the alumina support with Jie-macroporous structure, is urged
Agent adding hydrogen into resin activity is high, and activity stability is good, and service cycle is long.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Embodiment
A kind of method of hydrotreating of Petropols of the invention is described in further detail by the following examples.But this
A little embodiments are not regarded as limiting of the invention.
Primary raw material used in catalyst is prepared to originate：Reagent of the present invention is commercially available prod.
Raw material is cracking of ethylene C5 mixing Petropols, resin Gardener after desulfurization dechlorination and de- impurity treatment
Colourity is 9, bromine valency 18gBr/100g oil, softening point 119.
Embodiment 1
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water first, acetic acid is added dropwise afterwards, until
Chitosan dissolving is complete, obtains the acid solution containing expanding agent.A certain amount of phosphoric acid and potassium nitrate are weighed respectively, by phosphoric acid and potassium nitrate
It is dissolved completely in 70g distilled water and is made into the phosphorous and potassium aqueous solution.Weigh 350g boehmites powder and 20.0g sesbania powders add
Enter into kneader, and be well mixed, add the mixed solution of phosphoric acid and potassium nitrate, finally add the acid solution of chitosan-containing
Enter into boehmite powder to mediate uniformly, be clover shape by kneading-extruded moulding.Dried 8 hours at 120 DEG C,
700 DEG C are calcined 4 hours, obtain phosphorous and potassium alumina support 1.P in carrier 12O50.5wt%, K2O 1.8wt%.Have
The alumina support specific surface area of macroporous structure is shown in Table 1 with pore-size distribution.
Take 10.0g palladium bichlorides and 7.96g nickel phosphides to be added in 30ml distilled water, add ammoniacal liquor and adjust pH value after 3.0,
Diluted again with deionized water, wiring solution-forming is impregnated before the spherical alumina support 100g with macroporous structure, obtained catalyst
Body is calcined 6h after 120 DEG C of drying 6h at 450 DEG C, obtains the catalyst 1 of hydrogenation of petroleum resin.Catalyst 1 is mainly constituted：Oxygen
Change palladium 7.5wt%, nickel phosphide 3.0wt%, the aluminum oxide 89.5wt% with macroporous structure.
By catalyst 1 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, 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 carry out under certain process conditions hydrogenation reaction, hydrogenated products
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 to be analyzed after reaction about 55h.Analysis result shows product
Gardener colourities are 0, bromine valency 0.52gBr/100g oil, softening point 100.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 0.84gBr/100g oil, softening point 104.As a result show：
The activity of catalyst reaction prepared by the invention is higher, and activity stability is good, and overall performance is good.
Embodiment 2
8.0g water soluble chitosan expanding agents are added in 50 DEG C of deionized water, acetic acid is added dropwise afterwards, until shell gathers
Sugar dissolving is complete, obtains the acid solution containing expanding agent.A certain amount of phosphoric acid and potassium nitrate are weighed respectively, phosphoric acid and potassium nitrate is complete
It is dissolved in 70g distilled water and is made into the phosphorous and potassium aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powders are added
Into kneader, and it is well mixed, adds the mixed solution of phosphoric acid and potassium nitrate, finally adds the acid solution of chitosan-containing
Mediated into boehmite powder uniformly, be clover shape by kneading-extruded moulding.8 hours, 700 are dried at 120 DEG C
DEG C roasting 4 hours, obtains phosphorous and potassium alumina support 2.P in carrier 22O50.8%, K2O 1.0%
Phosphorus and potassium is recycled to be modified carrier surface, the aqueous solution spray of configuration phosphoric acid and potassium nitrate has macropore
The alumina support of structure, is dried 8 hours, 700 DEG C of roastings obtain used additives phosphorus for 4 hours and potassium carries out surface modification through 120 DEG C
Alumina support 2, carrier surface P2O5And K2O content is internal P2O5And K21.1 times of O content.With macroporous structure
Alumina support specific surface area is shown in Table 1 with pore-size distribution.
Take palladium bichloride and nickel phosphide to be added in 30ml distilled water, add ammoniacal liquor and adjust pH value after 3.0, then use deionization
Water dilutes, and wiring solution-forming impregnates the spherical alumina support 100g with macroporous structure, and obtained catalyst precursor is at 120 DEG C
Dry after 6h in 500 DEG C of roasting 6h, obtain the catalyst 2 of hydrogenation of petroleum resin.Catalyst 2 is mainly constituted：Palladium oxide
3.5wt%, nickel phosphide 8.0wt%, the alumina support 88.5wt% with macroporous structure.
By catalyst 2 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, 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 carry out under certain process conditions hydrogenation reaction, hydrogenated products
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 to be analyzed after reaction about 55h.Analysis result shows product
Gardener colourities are 0, bromine valency 0.85gBr/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, bromine valency 0.91gBr/100g oil, softening point 102.As a result show：Should
Activity height, the activity stability for inventing the catalyst reaction of the catalyst surface modification prepared are good, and overall performance is excellent.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan formic acid liquid magnetic stirrer 30 minutes.Obtain the oxygen with macroporous structure
Change alumina supporter 3.The content of adjuvant component phosphorus and potassium accounts for the percentage composition respectively P of carrier quality in carrier2O51.8wt%, K2O
2.0wt%.Its specific surface area is shown in Table 1 with pore-size distribution.
Take palladium bichloride and nickel phosphide to be added in 30ml distilled water, add ammoniacal liquor and adjust pH value after 3.0, then use deionization
Water dilutes, and wiring solution-forming impregnates the spherical alumina support 100g with macroporous structure, and specific steps are with embodiment 1.Catalysis
Agent is calcined 6.0h after 120 DEG C of drying 6h at 550 DEG C, obtains hydrogenation catalyst 3.Catalyst 3 is mainly constituted：Palladium oxide
2.5wt%, nickel phosphide 10.5wt%, the alumina support 87.0wt% with macroporous structure.
By catalyst 3 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, 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 carry out under certain process conditions hydrogenation reaction, hydrogenated products
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 to be analyzed after reaction about 55h, analysis result shows product
Gardener colourities are 0, bromine valency 0.95gBr/100g oil, softening point 103.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 104.As a result show：
Activity height, the activity stability of catalyst reaction prepared by the invention are good, and overall performance is good.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 1.Difference is water soluble chitosan expanding agent being replaced by
Water-insoluble chitosan expanding agent, chitosan acetic acid solution ultrasonic oscillation 15 minutes.Obtain the aluminum oxide with macroporous structure
Carrier.The content of adjuvant component phosphorus and potassium accounts for the percentage composition respectively P of carrier quality in carrier2O50.5wt%, K2O
0.7wt%.Recycle phosphorus and potassium to be modified carrier surface, obtain carrier 4, the surface P of carrier 42O5And K2O content is interior
Portion P2O5And K21.5 times of O content.The specific surface area of alumina support 4 with macroporous structure is shown in Table 1 with pore-size distribution.
Take palladium bichloride and nickel phosphide to be added in 30ml distilled water, add ammoniacal liquor and adjust pH value after 3.0, then use deionization
Water dilutes, and is made into maceration extract and impregnates the spherical alumina support 100g with macroporous structure, specific steps are with embodiment 1.Urge
Agent is calcined 4.0h after 120 DEG C of drying 6h at 600 DEG C, obtains hydrogenation catalyst 4.Catalyst 4 is mainly constituted：Palladium oxide
3.5wt%, nickel phosphide 4.0wt%, the alumina support 93.5wt% with macroporous structure.
By catalyst 4 and the small porcelain balls 1 of φ 1mm:It is fitted into after 1 mixing in 100ml fixed bed reactors, 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 carry out under certain process conditions hydrogenation reaction, hydrogenated products
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 to be analyzed after reaction about 55h.Analysis result shows product
Gardener colourities are 0, bromine valency 1.05gBr/100g oil, softening point 103.Sampling analysis result table after 500h long-term operations
It is bright：The Gardener colourities of C 5 petroleum resin product are 0, bromine valency 1.11gBr/100g oil, softening point 103.As a result show：Should
The active high stability of catalyst reaction for inventing the catalyst surface modification prepared is good, and overall performance is excellent.
Table 1 has the alumina support specific surface area and pore-size distribution of macroporous structure
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
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (9)
1. a kind of method of hydrotreating of Petropols, 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, carries out hydrogenation reaction under the reaction process condition of setting, hydrogenated products with
Performance evaluation is carried out after solvent separation；
Described catalyst active center is palladium oxide and nickel phosphide, the alumina support 75.0- with macroporous structure
96.0wt%, carrier uses chitosan as expanding agent；Active component palladium oxide 1.0-10.0wt%, nickel phosphide 3.0-
15.0wt%；
The preparation method of described catalyst, comprises the following steps：
Soluble-salt and nickel phosphide containing palladium are made into maceration extract, alumina support of the dipping with macroporous structure, at 120 DEG C
Roasting obtains the catalyst of hydrogenation of petroleum resin for 6-8 hours at drying 6 hours, 450-650 DEG C；
The preparation method of the alumina support, comprises the following steps：First, acid solution acidified chitosan is used, then will intend thin
Diaspore and sesbania powder are added in kneader and are well mixed, and add the mixed solution of phosphoric acid and magnesium nitrate, will finally contain shell
The acid solution of glycan, which is added in boehmite powder, to be mediated uniformly, and the addition of the acid solution containing expanding agent is the thin water aluminium of plan
The 0.1-8wt% of stone, by extrusion-shaping-drying-roasting, obtains the alumina support with macroporous structure；
Described hydrogenation of petroleum resin reacts, and its process conditions is：180-270 DEG C of reaction temperature, reaction pressure 6.0-
15.0MPa, hydrogen to oil volume ratio 100-400, volume space velocity 0.2-7.0h-1。
2. a kind of method of hydrotreating of Petropols according to claim 1, it is characterised in that：Described fixed bed reaction
Device, is fixed bed adiabatic reactor or fixed bed isothermal reactor；
Described hydrogenation of petroleum resin reacts, and its process conditions is：190-220 DEG C of temperature, reaction pressure 7.0-10.0MPa, hydrogen
Oil volume is than 150-350, volume sky 1.0-3.0h-1。
3. a kind of method of hydrotreating of Petropols according to claim 1, it is characterised in that：
The composition of described catalyst is with oxidation material gauge, including following component：Alumina support with macroporous structure is accounted for
83.0-94.5wt%, active component palladium oxide 2.5-9.0wt%, nickel phosphide 4.0-12.0wt%；
Containing adjuvant component phosphorus and potassium in the aluminum oxide with macroporous structure, the content of adjuvant component phosphorus and potassium accounts for carrier matter
The percentage composition of amount is respectively P2O50.1-2.5wt%, K2O 0.1-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-
75%, pore volume 0.8-2.0ml/g, specific surface area 250-300m2/g。
4. a kind of method of hydrotreating of Petropols according to claim 3, it is characterised in that：
The alumina support with macroporous structure, is modified using phosphorus and potassium to carrier surface：Configure phosphoric acid and nitre
Alumina support of the aqueous solution spray with macroporous structure of sour potassium, obtains used additives phosphorus through drying, roasting and potassium carries out surface
P in modified alumina support, alumina support of the control with macroporous structure2O5And K2O content is respectively in 0.1-2.5wt%
In the range of 0.1-2.5wt%, and make carrier surface P2O5And K2O content is internal P2O5And K2The 1.1-1.5 of O content
Times.
5. a kind of method of hydrotreating of Petropols according to claim 3, it is characterised in that：The hole of the alumina support
Footpath is distributed in 65-150nm, macropore ratio 5-65%, pore volume 0.8-1.3ml/g.
6. a kind of method of hydrotreating of Petropols according to claim 3, it is characterised in that：Alumina support also contains simultaneously
There is meso-hole structure, macropore range is in 2-50nm, mesoporous ratio 15-75%.
7. a kind of method of hydrotreating of Petropols according to claim 1, it is characterised in that：The acid solution acidifying shell gathers
The process of sugar is as follows：Chitosan expanding agent is added in 30-95 DEG C of deionized water first, acid is added dropwise afterwards, until shell gathers
Sugar dissolving is complete, obtains the acid solution containing expanding agent.
8. a kind of method of hydrotreating of Petropols according to claim 7, it is characterised in that：It is described acid for acetic acid, formic acid,
One or more in malic acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic agitation.
9. a kind of method of hydrotreating of Petropols according to claim 1, it is characterised in that：Described fixed bed reactors
For fixed bed isothermal reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408951.6A CN107082847B (en) | 2017-06-02 | 2017-06-02 | A kind of method of hydrotreating of Petropols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408951.6A CN107082847B (en) | 2017-06-02 | 2017-06-02 | A kind of method of hydrotreating of Petropols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107082847A true CN107082847A (en) | 2017-08-22 |
| CN107082847B CN107082847B (en) | 2019-01-25 |
Family
ID=59608612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710408951.6A Active CN107082847B (en) | 2017-06-02 | 2017-06-02 | A kind of method of hydrotreating of Petropols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107082847B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127506A (en) * | 1976-03-12 | 1978-11-28 | California Institute Of Technology | Photochemical preparation of olefin addition catalysts |
| WO1999006146A2 (en) * | 1997-07-29 | 1999-02-11 | E.I. Du Pont De Nemours And Company | Supported diols and supported bis(phosphorus) ligands |
| JP2003126698A (en) * | 2001-10-25 | 2003-05-07 | Mitsubishi Rayon Co Ltd | Catalyst for hydrogenating unsaturated polymer and manufacturing method for hydrogenated polymer latex |
| CN101633713A (en) * | 2008-07-24 | 2010-01-27 | 朗盛公司 | Process for the continuous hydrogenation of carbon-carbon double bonds in an unsaturated polymer to produce a hydrogenated polymer |
| CN105749972A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | Petroleum resin hydrogenation catalyst and preparation method and application thereof |
| CN106563461A (en) * | 2016-10-31 | 2017-04-19 | 北京思信通科技有限公司 | Petroleum resin hydrotreating method |
-
2017
- 2017-06-02 CN CN201710408951.6A patent/CN107082847B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127506A (en) * | 1976-03-12 | 1978-11-28 | California Institute Of Technology | Photochemical preparation of olefin addition catalysts |
| WO1999006146A2 (en) * | 1997-07-29 | 1999-02-11 | E.I. Du Pont De Nemours And Company | Supported diols and supported bis(phosphorus) ligands |
| JP2003126698A (en) * | 2001-10-25 | 2003-05-07 | Mitsubishi Rayon Co Ltd | Catalyst for hydrogenating unsaturated polymer and manufacturing method for hydrogenated polymer latex |
| CN101633713A (en) * | 2008-07-24 | 2010-01-27 | 朗盛公司 | Process for the continuous hydrogenation of carbon-carbon double bonds in an unsaturated polymer to produce a hydrogenated polymer |
| CN105749972A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | Petroleum resin hydrogenation catalyst and preparation method and application thereof |
| CN106563461A (en) * | 2016-10-31 | 2017-04-19 | 北京思信通科技有限公司 | Petroleum resin hydrotreating method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107082847B (en) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102451765B (en) | Preparation method for composite oxide carrier | |
| CN107011939A (en) | A kind of method of distillate hydrogenation dearsenification | |
| CN105457678B (en) | Supported heteropoly compound catalyst, preparation method and applications | |
| WO2011103698A1 (en) | Hydro refining catalyst | |
| CN103285909B (en) | A kind of hydrocracking catalyst containing mesoporous-microporomolecular molecular sieve and preparation method thereof | |
| CN109622024B (en) | Method for preparing supported NiMo/ZSM-5 hydrogenation catalyst by eutectic method | |
| CN110142044B (en) | Petroleum resin hydrogenation catalyst, and preparation method and application thereof | |
| CN104437581A (en) | Catalyst for acrylic acid synthesis and preparation method of catalyst | |
| CN103506130B (en) | A kind of Catalysts and its preparation method of synthesis of methyl mercaptan | |
| CN109364956A (en) | A kind of preparation method and applications of high activity molybdenum sulfide-zirconia catalyst | |
| CN107118795B (en) | A kind of method of hydrotreating of reforming raffinate oil | |
| CN109046362A (en) | A kind of preparation method and applications of carbon-coated nano CuZnAl catalyst | |
| CN106994351A (en) | A kind of distillate hydrogenation dearsenic catalyst and preparation method | |
| CN109847793A (en) | A kind of method of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst | |
| CN107082847B (en) | A kind of method of hydrotreating of Petropols | |
| CN102451769B (en) | Preparation method of composite oxide adhesive | |
| CN107051430B (en) | A kind of catalyst and preparation method of hydrogenation of petroleum resin | |
| CN105381816B (en) | A kind of catalyst for hydro-upgrading and its application | |
| CN107185560A (en) | A kind of olefin oligomerization catalyst and preparation method | |
| CN107159278A (en) | A kind of method of olefin(e) oligomerization | |
| CN107638888A (en) | New catalyst and preparation method thereof used in one kind production MEK | |
| CN102319571A (en) | Catalyst for catalyzing hydrocracking of biomass oil and preparation method and application thereof | |
| CN108722409A (en) | Mesoporous copper-based aluminium oxide catalyst, preparation method and application | |
| CN106622268B (en) | A kind of slurry bed hydrogenation catalyst and preparation method thereof | |
| CN106902878A (en) | It is a kind of for gasoline, coal tar hydrorefining desulfurization, the catalyst of denitrogenation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |