CN107082847B - A kind of method of hydrotreating of Petropols - Google Patents
A kind of method of hydrotreating of Petropols Download PDFInfo
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- CN107082847B CN107082847B CN201710408951.6A CN201710408951A CN107082847B CN 107082847 B CN107082847 B CN 107082847B CN 201710408951 A CN201710408951 A CN 201710408951A CN 107082847 B CN107082847 B CN 107082847B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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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
- 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
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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
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
The invention discloses a kind of method of hydrotreating of Petropols, using fixed bed reactors；The catalyst is the loaded catalyst that activated centre is palladium and nickel phosphide, and carrier is the alumina support with macroporous structure, and carrier uses chitosan as expanding agent.Hydrogenation process conditions are as follows: 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.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 have macroporous structure aluminium oxide using a kind of
For the hydrogenation of petroleum resin catalyst of carrier, reacted for hydrogenation of petroleum resin.
Background technique
Thermoplastic resin of the C5 and C9 fraction Jing Guo polymerization in cracking of ethylene by-product, 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 acid and alkali, weatherability, light fastness aging, are widely used in paint, coating, glue
The fields such as mixture and rubber.Currently, domestic petroleum resin is influenced by raw material composition, product is generally in light yellow or even reddish brown
Color, photostability is poor, can not limit its application as the raw material of high-end product.By being catalyzed to Petropols
Add hydrogen, molecule internal double bond and phenyl ring can be made to be saturated, while removing remaining halide and sulphur, nitrogen impurity in resin.After adding hydrogen
The general white or Transparent color of Petropols, and weatherability, adhesiveness, photo and thermal stability etc. are significantly improved, and are expanded
The application range of Petropols, improves the application added value of Petropols.Currently, foreign oil adding hydrogen into resin technology is
It obtains industrial application and popularization, the hydrogenation of petroleum resin one of the eighties, developed countries reaches 6.6 ten thousand tons/year, represent 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 significant
Promoted, cracking c5, C9 fraction quantity be increasing.This part resource is efficiently used, causes domestic scientific research personnel's
Pay attention to, and gradually increases research dynamics in the later period nineties.Supported nickel catalyst obtains larger concern simultaneously since cost is relatively low for it
Be widely studied, carrier mainly has aluminium oxide, magnesia, active carbon or a various composite materials, but the catalyst developed by
In there is hydrogenation activity difference, it is not well used always.
For the composite material of zinc oxide and aluminium oxide frequently as the carrier material of catalyst, application field is extensive.Spinel-type
Composite oxides are a kind of up-and-coming inorganic non-metallic materials, have a series of good characteristics and are widely used in height
The fields such as adiabator, catalyst and catalyst carrier.The common preparation method of the domestic and international material includes infusion process, mechanical mixture
Method, coprecipitation and peptisation.Wherein, since infusion process and mechanical mixing use alumina material as predecessor, pass through
The specific surface area of alumina material is adjusted, both methods can prepare the composite material of high specific surface area, but due to multiple
Aluminium oxide and zinc oxide interaction in condensation material is weaker, and the loss of zinc oxide is easy to produce in use process, is usually to adopt
The two is promoted to form spinelle with the method for high-temperature roasting to avoid the loss of zinc oxide；And coprecipitation and peptisation use and contain
The compound of aluminum and zinc prepares zinc-aluminium precursor by precipitating or peptization, and it is stronger that aluminum and zinc passes through reaction generation during the preparation process
Interaction can be lost to avoid the zinc oxide in use process, 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, adopts using active carbon or silica as carrier
It is loaded with equi-volume impregnating；CN103386308A discloses a kind of C5 hydrogenation of petroleum resin Raney nickel, with activity
Charcoal loads Ni, and the auxiliary agents such as addition Zn, Co form amorphous alloy nano particle, and reaction conversion ratio and selectivity increase；Patent
CN102935367A discloses a kind of palladium base C5 hydrogenation of petroleum resin catalyst, with aluminium oxide, titanium oxide composite carrier load palladium,
Molybdenum/tungsten active component, the mass fraction of supported palladium are 0.2%-0.4%, which has low temperature hydrogenation activity, good 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, for catalyst using nano particle as active component, magnesia is carrier,
Nano nickel/magnesia catalyst of preparation has the characteristics that catalytic activity is high, stability is good, is easily isolated, in mild reaction
Under the conditions of Petropols are carried out plus hydrogen, the degree of unsaturation of resin significantly reduces, 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 nickel load diatomite
Agent, and the elements such as barium, calcium, magnesium, copper are added in system and are modified.
Existing main problem hydrogenation process conditions are harsh during existing hydrogenation of petroleum resin, are hydrogenation resin softening points
Low, the anti-impurity ability of hydrogenation catalyst is poor, activity stability is poor.
Summary of the invention
The present invention provides a kind of method of hydrotreating of Petropols, produce high-grade Petropols for hydrogenation of petroleum resin and produce
Product.The present invention includes the following steps:
Load there is into the Catalyst packing of palladium and nickel phosphide in fixed bed reactors, is started after airtight experiment is qualified into warp
The mixing C 5 petroleum resin raw material of solvent dissolution, 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 meter: the alumina support 75.0-96.0wt% with macroporous structure,
Active component palladium oxide 1.0-10.0wt%, nickel phosphide 3.0-15.0wt%；
Preferably, 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%.
The hydrogenation of petroleum resin method for preparing catalyst, includes the following steps:
By the soluble-salt containing palladium, wiring solution-forming, dipping have the alumina support of macroporous structure together with nickel phosphide,
It is roasted 6-8 hours at drying 6 hours, 450-650 DEG C at 120 DEG C and obtains the catalyst of hydrogenation of petroleum resin.
Fixed bed reactors of the present invention, it is preferably solid for fixed bed adiabatic reactor or fixed bed isothermal reactor
Fixed bed isothermal reactor.
The hydrogenation of petroleum resin reaction, process conditions are as follows: 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, synthesizing has greatly
The alumina support of pore structure.
The alumina support with macroporous structure contains adjuvant component phosphorus and potassium, adjuvant component phosphorus and potassium in carrier
Content to account for the percentage composition of carrier quality be respectively P2O50.1-2.5wt%, K2O0.1-2.5wt%, pore-size distribution 60-
180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, hole holds 0.8-2.0ml/g, preferably 0.8-1.3ml/g
Or preferably 1.6-2.0ml/g, specific surface area 250-300m2/ g, carrier use chitosan as expanding agent.
The alumina support with macroporous structure, aperture can pass through the additional amount and expanding agent of variation expanding agent
Molecular size range be adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-160nm,
The ranges such as 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the ranges such as 35-50%, 55-75%.
The preparation method of the alumina support with macroporous structure, includes the following steps: firstly, being acidified with acid solution
Then boehmite and sesbania powder are added in kneader and are uniformly 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 is mediated uniformly, the acid solution containing expanding agent
Additional amount be boehmite 0.1-8wt%, preferably 0.2-5.0wt% obtained by extrusion-molding-drying-roasting
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 later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The additional amount of acid is advisable with that can be completely dissolved chitosan.It can also
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.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Wave concussion or magnetic agitation, expanding agent good dispersion, alumina support is more prone to produce macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.
The additional amount of the sesbania powder is the 0.1-7wt% of boehmite.
It mediates or extrusion technique is that the configured acid solution containing expanding agent is added in sesbania powder and boehmite
Be uniformly mixed, later extrusion, molding, by 100-160 DEG C drying 3-9 hours, 650-800 DEG C roasting 4-8 hours, finally obtain
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 a kind of big containing Jie-in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%
The alumina support in hole, and aperture is not uniform aperture structure.
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 excessively high, and preferably configuration concentration is lower than phosphoric acid and potassium nitrate when preparing carrier
Aqueous solution sprays carrier surface, preferably carries out carrier surface modification as follows: configuration phosphoric acid and potassium nitrate it is water-soluble
Liquid spray has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and potassium carries out the modified oxidation in surface
Alumina supporter controls P in the alumina support with macroporous structure2O5And K2O content is respectively in 0.1-2.5wt% and 0.1-
In the range of 2.5wt%, and the content of carrier surface P2O5 and K2O is made to be 1.1-1.5 times of internal P2O5 and K2O content.
Compared with prior art, the invention has the following advantages that
1, for alumina support of the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is suitble to industrialized production.The obtained alumina support with macroporous structure, pore size is adjustable, and macropore ratio can
Effectively to control.And carrier also contains mesoporous, is a kind of Jie-macropore alumina supporter.
2, the present invention can also introduce phosphorus and potassium in alumina support, the obtained carrying alumina with macroporous structure
Body, the carrier are prepared into hydrogenation of petroleum resin catalyst, have better adding hydrogen into resin activity, selectivity and stability.
3, the alumina support with macroporous structure that the present invention obtains, using phosphorus and potassium to the oxidation with macroporous structure
Alumina supporter surface is modified, and makes carrier surface P2O5And K2The content of O is internal P2O5And K21.1-1.5 times of O content.It adopts
Carrier surface is modified with the mode of spray, is capable of the partial pore of effective peptization carrier surface, advantageously reduces in this way
The micropore ratio of carrier surface improves carrier surface Jie-macropore ratio, and carrier surface is promoted to produce more active sites loads
Center effectively improves catalyst hydrogenation activity.Dipping method should not be used to the improvement of carrier surface, impregnated carrier surface can make greatly
Amount moisture enters carrier, and intensity is deteriorated, and is not achieved and improves carrier surface Jie-macropore ratio purpose.
4, hydrogenation of petroleum resin catalyst carrier provided by the invention is that have Jie-macroporous structure alumina support, is urged
Agent adding hydrogen into resin activity is high, and activity stability is good, and operation cycle is long.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Specific embodiment
A kind of method of hydrotreating of Petropols of the present invention is described in further detail by the following examples.But this
A little embodiments are not regarded as limiting of the invention.
Prepare primary raw material source used in catalyst: reagent of the present invention is commercial product.
Raw material is cracking of ethylene C5 mixing Petropols, resin Gardener after desulfurization dechlorination and de- impurity treatment
Coloration is 9, bromine valency 18gBr/100g oil, softening point 119.
Embodiment 1
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water first, acetic acid is added dropwise later, until
Chitosan dissolution completely, 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 phosphorous and potassium aqueous solution.It weighs 350g boehmite powder and 20.0g sesbania powder adds
Enter into kneader, and be uniformly mixed, add the mixed solution of phosphoric acid and potassium nitrate, finally adds the acid solution of chitosan-containing
Enter into boehmite powder to mediate uniformly, is clover shape by kneading-extruded moulding.It is 8 hours dry at 120 DEG C,
700 DEG C roast 4 hours, obtain phosphorous and potassium alumina support 1.P in carrier 12O50.5wt%, K2O 1.8wt%.Have
The alumina support specific surface area and pore-size distribution of macroporous structure are shown in Table 1.
It takes 10.0g palladium chloride and 7.96g nickel phosphide to be added in 30ml distilled water, ammonium hydroxide is added and adjusts pH value after 3.0,
It is diluted again with deionized water, the spherical alumina support 100g with macroporous structure of wiring solution-forming dipping, before obtained catalyst
Body, in 450 DEG C of roasting 6h, obtains the catalyst 1 of hydrogenation of petroleum resin after 120 DEG C of drying 6h.Catalyst 1 mainly forms: oxygen
Change palladium 7.5wt%, nickel phosphide 3.0wt%, the aluminium oxide 89.5wt% with macroporous structure.
It is fitted into 100ml fixed bed reactors after catalyst 1 is mixed with the small porcelain ball 1:1 of φ 1mm, filling sequence is φ
The small porcelain ball of 1mm, catalyst porcelain ball mixture, φ 1mm small porcelain ball after Catalyst packing, carry out airtight experiment, airtight qualification
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and carries out hydrogenation reaction, hydrogenated products under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are as follows: 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 is the result shows that product
Gardener coloration is 0, bromine valency 0.52gBr/100g oil, softening point 100.Sampling analysis result table after 500h long-term operation
Bright: the Gardener coloration of C 5 petroleum resin product is 0.5, bromine valency 0.84gBr/100g oil, softening point 104.The result shows that:
The activity of the catalyst reaction of invention preparation is higher, and activity stability is good, and overall performance is good.
Embodiment 2
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water, acetic acid is added dropwise later, until shell is poly-
Sugar dissolution completely, 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 phosphorous and potassium aqueous solution.It weighs 350g boehmite powder and 20.0g sesbania powder is added
It into kneader, and is uniformly mixed, adds the mixed solution of phosphoric acid and potassium nitrate, finally the acid solution of chitosan-containing is added
It is mediated into boehmite powder uniformly, is clover shape by kneading-extruded moulding.It is 8 hours dry at 120 DEG C, 700
DEG C roasting 4 hours, obtain 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 for configuring phosphoric acid and potassium nitrate has macropore
The alumina support of structure, 8 hours dry through 120 DEG C, 700 DEG C of roastings obtain used additives phosphorus for 4 hours and potassium carries out surface and is modified
Alumina support 2, carrier surface P2O5And K2The content of O is internal P2O5And K21.1 times of O content.With macroporous structure
Alumina support specific surface area and pore-size distribution are shown in Table 1.
It takes palladium chloride and nickel phosphide to be added in 30ml distilled water, ammonium hydroxide is added and adjusts pH value after 3.0, then uses deionization
Water dilution, the spherical alumina support 100g with macroporous structure of wiring solution-forming dipping, obtained catalyst precursor is at 120 DEG C
In 500 DEG C of roasting 6h after drying 6h, the catalyst 2 of hydrogenation of petroleum resin is obtained.Catalyst 2 mainly forms: palladium oxide
3.5wt%, nickel phosphide 8.0wt%, the alumina support 88.5wt% with macroporous structure.
It is fitted into 100ml fixed bed reactors after catalyst 2 is mixed with the small porcelain ball 1:1 of φ 1mm, filling sequence is φ
The small porcelain ball of 1mm, catalyst porcelain ball mixture, φ 1mm small porcelain ball after Catalyst packing, carry out airtight experiment, airtight qualification
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and carries out hydrogenation reaction, hydrogenated products under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are as follows: 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 is the result shows that product
Gardener coloration is 0, bromine valency 0.85gBr/100g oil, softening point 102.Sampling analysis result table after 500h long-term operation
Bright: the Gardener coloration of C 5 petroleum resin product is 0, bromine valency 0.91gBr/100g oil, softening point 102.The result shows that: it should
Activity height, the activity stability for inventing the catalyst reaction of the catalyst surface modification of preparation are good, and overall performance is excellent.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan formic acid liquid was with magnetic stirrer 30 minutes.Obtain the oxygen with macroporous structure
Change alumina supporter 3.The percentage composition that the content of adjuvant component phosphorus and potassium accounts for carrier quality in carrier is respectively P2O51.8wt%, K2O
2.0wt%.Its specific surface area and pore-size distribution are shown in Table 1.
It takes palladium chloride and nickel phosphide to be added in 30ml distilled water, ammonium hydroxide is added and adjusts pH value after 3.0, then uses deionization
Water dilution, the spherical alumina support 100g with macroporous structure of wiring solution-forming dipping, specific steps are the same as embodiment 1.Catalysis
Agent, in 550 DEG C of roasting 6.0h, obtains hydrogenation catalyst 3 after 120 DEG C of drying 6h.Catalyst 3 mainly forms: palladium oxide
2.5wt%, nickel phosphide 10.5wt%, the alumina support 87.0wt% with macroporous structure.
It is fitted into 100ml fixed bed reactors after catalyst 3 is mixed with the small porcelain ball 1:1 of φ 1mm, filling sequence is φ
The small porcelain ball of 1mm, catalyst porcelain ball mixture, φ 1mm small porcelain ball after Catalyst packing, carry out airtight experiment, airtight qualification
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and carries out hydrogenation reaction, hydrogenated products under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are as follows: 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 is the result shows that product
Gardener coloration is 0, bromine valency 0.95gBr/100g oil, softening point 103.Sampling analysis result table after 500h long-term operation
Bright: the Gardener coloration of C 5 petroleum resin product is 0.5, bromine valency 1.21gBr/100g oil, softening point 104.The result shows that:
The activity of the catalyst reaction of invention preparation is high, activity stability is good, and overall performance is good.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 1.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan acetic acid solution was with ultrasonic oscillation 15 minutes.Obtain the aluminium oxide with macroporous structure
Carrier.The percentage composition that the content of adjuvant component phosphorus and potassium accounts for carrier quality in carrier is respectively P2O50.5wt%, K2O
0.7wt%.It recycles phosphorus and potassium to be modified carrier surface, obtains carrier 4,4 surface P of carrier2O5And K2The content of O is interior
Portion P2O5And K21.5 times of O content.4 specific surface area of alumina support and pore-size distribution with macroporous structure are shown in Table 1.
It takes palladium chloride and nickel phosphide to be added in 30ml distilled water, ammonium hydroxide is added and adjusts pH value after 3.0, then uses deionization
Water dilution is made into the spherical alumina support 100g with macroporous structure of maceration extract dipping, and specific steps are the same as embodiment 1.It urges
Agent, in 600 DEG C of roasting 4.0h, obtains hydrogenation catalyst 4 after 120 DEG C of drying 6h.Catalyst 4 mainly forms: palladium oxide
3.5wt%, nickel phosphide 4.0wt%, the alumina support 93.5wt% with macroporous structure.
It is fitted into 100ml fixed bed reactors after catalyst 4 is mixed with the small porcelain ball 1:1 of φ 1mm, filling sequence is φ
The small porcelain ball of 1mm, catalyst porcelain ball mixture, φ 1mm small porcelain ball after Catalyst packing, carry out airtight experiment, airtight qualification
Start afterwards into the C 5 petroleum resin raw material being dissolved by the solvent, and carries out hydrogenation reaction, hydrogenated products under certain process conditions
Carry out solvent and product decompression separation.
The process conditions of C 5 petroleum resin hydrogenation reaction are as follows: 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 is the result shows that product
Gardener coloration is 0, bromine valency 1.05gBr/100g oil, softening point 103.Sampling analysis result table after 500h long-term operation
Bright: the Gardener coloration of C 5 petroleum resin product is 0, bromine valency 1.11gBr/100g oil, softening point 103.The result shows that: it should
The catalyst reaction activity high stability for inventing the catalyst surface modification of preparation 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, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (8)
1. a kind of method of hydrotreating of Petropols, which comprises the steps of:
Load there is into the Catalyst packing of palladium oxide and nickel phosphide in fixed bed reactors, is started after airtight experiment is qualified into warp
The mixing C 5 petroleum resin raw material of solvent dissolution, carries out hydrogenation reaction under the reaction process condition of setting, hydrogenated products with
Performance evaluation is carried out after solvent separation；
The catalyst active center is palladium oxide and nickel phosphide, the alumina support 75.0- with macroporous structure
96.0wt%, carrier use chitosan as expanding agent；Active component palladium oxide 1.0-10.0wt%, nickel phosphide 3.0-
15.0wt%；
The preparation method of the catalyst, includes the following steps:
By containing palladium soluble-salt and nickel phosphide be made into maceration extract, the alumina support with macroporous structure is impregnated, at 120 DEG C
It is roasted 6-8 hours at 6 hours, 450-650 DEG C dry and obtains the catalyst of hydrogenation of petroleum resin；
The preparation method of the alumina support includes the following steps: firstly, then will be intended thin with acid solution acidified chitosan
Diaspore and sesbania powder are added in kneader and are uniformly 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 additional amount of the acid solution containing expanding agent is to intend thin water aluminium
The 0.1-8wt% of stone obtains the alumina support with macroporous structure by extrusion-molding-drying-roasting；
The alumina support with macroporous structure, is modified carrier surface using phosphorus and potassium: configuration phosphoric acid and nitre
The aqueous solution spray of sour potassium has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and potassium carries out surface
Modified alumina support controls P in the alumina support 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 K2The content of O is internal P2O5And K2The 1.1-1.5 of O content
Times, pore-size distribution 60-180nm, macropore ratio 2-75%, hole hold 0.8-2.0ml/g, specific surface area 250-300m2/g；
The hydrogenation of petroleum resin reaction, process conditions are as follows: 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: the fixed bed reaction
Device is fixed bed adiabatic reactor or fixed bed isothermal reactor；
The hydrogenation of petroleum resin reaction, process conditions are as follows: 190-220 DEG C of temperature, reaction pressure 7.0-10.0MPa, hydrogen
Oil volume ratio 150-350, volume sky 1.0-3.0h-1。
3. a kind of method of hydrotreating of Petropols according to claim 2, it is characterised in that: the fixed bed reactors
For fixed bed isothermal reactor.
4. a kind of method of hydrotreating of Petropols according to claim 1, it is characterised in that:
The composition of the catalyst is with oxidation material meter, including following component: 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%；
Contain adjuvant component phosphorus and potassium in the aluminium 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%.
5. a kind of method of hydrotreating of Petropols according to claim 1, it is characterised in that: the hole of the alumina support
Diameter is distributed in 65-150nm, macropore ratio 5-65%, and hole holds 0.8-1.3ml/g.
6. a kind of method of hydrotreating of Petropols according to claim 1, 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 acidification shell is poly-
The process of sugar is as follows: chitosan expanding agent being added in 30-95 DEG C of deionized water first, acid is added dropwise later, until shell is poly-
Sugar dissolution completely, 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 be acetic acid, formic acid,
One or more of malic acid or lactic acid, chitosan acid solution ultrasonic oscillation or magnetic agitation.
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| 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 |
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| 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 |
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