CN1962706A - Process for preparing hydrogenated C5/C9 copolymerized petroleum resin - Google Patents
Process for preparing hydrogenated C5/C9 copolymerized petroleum resin Download PDFInfo
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- CN1962706A CN1962706A CN 200610097805 CN200610097805A CN1962706A CN 1962706 A CN1962706 A CN 1962706A CN 200610097805 CN200610097805 CN 200610097805 CN 200610097805 A CN200610097805 A CN 200610097805A CN 1962706 A CN1962706 A CN 1962706A
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Abstract
The invention discloses a preparing method of hydrogenated C5/C9 copolymerized oil resin, which comprises the following steps: dissolving C5/C9 copolymer oil resin in the hydrogenation solvent; decoloring through adsorbing agent to proceed catalytic hydrogenating reaction with hydrogen in the fixed bed reactor at 220-270 Deg C under 2.0-8.0Mpa; setting the bulk air-speed at 0.1-1.0h-1 and hydrogen and oil rate at 300-3000:1; allocating the catalyst as load-patterned nickel catalyst with 35-50% Ni; adopting gamma-Al2O3 as carrier with specific area at 150-300m2/g and hole conpacitance at 0.2-0.4ml/g; decompressing hydrogenated product; distilling to recycle solvent to obtain the product.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenated petroleum resin, particularly relate to a kind of hydrogenation C
5/ C
9The preparation method of copolymerized petroleum resin.
Background technology
Petroleum resin are the C with the petroleum cracking by-product
5, C
9Cut is a raw material, and by the base polymer that catalyzed polymerization obtains, since the U.S. in 1945 at first successfully developed petroleum resin, its kind was more and more.Can be divided into five classes (1) C according to the raw materials used difference of its polymerization
5Aliphatic hydrocarbon resin is by C
5Cut makes; (2) C
9The aromatic hydrocarbon petroleum resin are by C
9Cut makes; (3) aromatic hydrocarbon-aliphatic hydrocarbon copolymer resins claims C again
5/ C
9Copolymerized petroleum resin; (4) dcpd resin is made and is claimed DCPD resin by dicyclopentadiene or its mixture; (5) hydrogenated petroleum resin.
China starts from 1964 to the research of petroleum resin, and China's oil resin overall throughput is more than 300,000 tons/year at present, and most of device industrial scale is little, technology is simple, is simply equipped, and kind is single, quality product is not high, particularly the product colour difference (light color 6
#～13
#, dark 14
#～18
#), main quality index instability such as softening temperature, range of application is narrow.At present can only in, use in low-grade paint, printing ink and the rubber item, and be used for the very few of aspects such as tackiness agent, marking paint and high-grade paint, printing ink, rubber item, main dependence on import.Sub-petrochemical industry limited-liability company and U.S. Eastman company are joint to have built 1.8 ten thousand tons of/year hydrogenation C along with raising
51.5 ten thousand tons of/year C of the joint construction of petroleum resin device and Shanghai petrochemical industry limited-liability company and U.S. Exxon company
5Being constructed and put into operation of large-scale plants such as petroleum resin device, the integral level of China's oil resin industry is significantly improved.
Petroleum resin have entered the epoch of technology competition, and just towards scale maximization, diversification of varieties, the direction of trade mark seriation develops the trend that petroleum resin are produced.What emphasize in recent years is to produce high softening-point, good weatherability, low viscous copolymer resin, to C
5, C
5/ C
9, C
9Resin requires light colorization more.High-quality petroleum resin on the world market, its colourity is less than 3
#, softening temperature generally adopts the hydrogen addition technology of petroleum resin more than 85 ℃.Hydrogenated petroleum resin possesses performance advantage at aspects such as colourity, thermostability, oxidation-resistance, good weatherability, no sensitizations of skin, at aspects such as adhesive of medical, electronic product assembling, colourless tackiness agent, polymer modifications important application is arranged.
U.S. Pat 4540480, US 4952639 disclose the hydrogenation of petroleum resin method, and the active ingredient of catalyst system therefor is precious metals such as palladium, platinum, rhenium, ruthenium.U.S. Pat 6458902 and world patent WO2004052955 disclose C
9Synthetic and the method for hydrotreating of petroleum resin.US 6458902 discloses, and can use the Fu-Ke catalyzer of non-phenols, under the situation of the molecular weight regulator that has or do not exist non-phenols, with C
9The resulting petroleum resin hydrogenation of cut polymerization, described non-phenols Fu-the Ke catalyzer is the mixture of boron trifluoride or boron trifluoride and ether.Chinese patent 97112026.9 has disclosed a kind of C
5Petroleum resin or C
9The method of hydrotreating of petroleum resin is that petroleum resin are dissolved in the resin solvent, is that 2～15MPa, temperature of reaction are under 220～350 ℃ the condition, with the NiO-WO of prevulcanized at hydrogen pressure
3-MgO/Al
2O
3The catalyzer contact, hydrogenation products obtains the purpose product through Separation and Recovery, and the used loaded catalyst that contains Ni and W consists of 1.0%～10.0%NiO, 15.0%～32.0%WO
3, 0.2%～3.5%MgO and balance carriers Al
2O
3, its specific surface is 120～250m
2/ g, pore volume are 0.4～0.9ml/g.
C
5/ C
9Copolymerized petroleum resin is the petroleum resin of putting on market in recent years, and it has C concurrently
5Color of resin more shallow (general 6
#～13
#), with good, heat-resisting, resistance to oxidation of natural rubber consistency and C
9The advantage that the petroleum resin softening temperature is high, moderate cost is widely used.General C
5/ C
9The production technique of copolymerized petroleum resin is cationoid polymerisation technology or thermal polymerization process, C
5And C
9Volume ratio be 1: 2.5～1: 3, form and aspect are generally 6
#～13
#(yellow), but have shortcomings such as unsaturated link(age) content height, smelly, the poor heat stability of flavor.The shortening technology is still the best method that addresses the above problem.At present, relevant C
5/ C
9The copolymerized petroleum resin shortening prepares hydrogenation C
5/ C
9The method of copolymerized petroleum resin is not seen public publish; And hydrogenation C home,
5/ C
9It is blank that the production of copolymer resins still belongs to.
The present invention discloses a kind of by C
5/ C
9Copolymerized petroleum resin prepares hydrogenation C
5/ C
9The method of copolymerized petroleum resin.
Summary of the invention
Technical problem
C
5/ C
9There are shortcomings such as unsaturated link(age) content height, smelly, the poor heat stability of flavor in copolymerized petroleum resin, and purpose of the present invention adopts the shortening technology to make C exactly
5/ C
9Two keys and part phenyl ring residual in the copolymerized petroleum resin are saturated, make that look shallow, flavor is low, softening temperature is higher, the hydrogenation C that bromine number is low, ageing-resistant
5/ C
9Copolymerized petroleum resin.
Technical scheme
C
5/ C
9Although copolymerized petroleum resin unsaturated link(age) content height, smelly, the poor heat stability of flavor are color more shallow (general 6
#～13
#), but the high-quality petroleum resin, its colourity is less than 3
#Form in the inside of molecular resin and the two keys of terminal some that keep behind the polymerization of unsaturated monomers in the color polymer raw of resin, because the existence of unsaturated link(age), also can influence the performance index such as softening temperature, thermostability of resin.Indenes, methyl indenes and naphthalene and cyclopentadiene, the polymerization of methyl cyclopentadiene fellowship, forming the overlength conjugated structure is C
5/ C
9The mechanism of mainly adding lustre in the copolymerized petroleum resin.By shortening, make C
5/ C
9Two keys and part phenyl ring residual in the copolymerized petroleum resin are saturated, reduce its bromine number, can make the hydrogenation C that look shallow, flavor is low, softening temperature is higher, ageing-resistant
5/ C
9Copolymerized petroleum resin.
The technical solution used in the present invention is:
A kind of hydrogenation C
5/ C
9The preparation method of copolymerized petroleum resin is with C
9/ C
9Copolymerized petroleum resin is dissolved in the organic solvent, adds the sorbent material decolouring, and resin solution after the decolouring and hydrogen enter and carries out catalytic hydrogenation reaction in the fixed-bed reactor, 220～270 ℃ of temperature of reaction, pressure 2.0～8.0MPa, volume space velocity 0.1～1.0h
-1, hydrogen-oil ratio 300～3000: 1; Hydrogenation catalyst adopts nickel catalyst carried, and Ni content is 35%～50% (wt%), and carrier is γ-Al
2O
3, specific surface is 150～300m
2/ g, pore volume are 0.2～0.4ml/g; Hydrogenation afterreaction product promptly gets hydrogenation C after reclaiming solvent
5/ C
9Copolymerized petroleum resin.
Described organic solvent can select that petroleum resin are had the solvent that can keep liquid phase under stronger dissolving power and the reaction conditions, C
5/ C
9Copolymerized petroleum resin is dissolved in this organic solvent, and the concentration of resin solution can be selected in its solubility range.Solvent can not only suppress the DeR in the hydrogenation process, and can make the resin desorption on catalyzer as early as possible behind the hydrogenation, reducing coking, thereby prolongs the work-ing life of catalyzer.Be used to realize organic solvent of the present invention, include but not limited to normal heptane, octane-iso, trimethyl-cyclohexane etc.The contriver has measured C under normal temperature (25 ℃)
5/ C
9Copolymerized petroleum resin is at normal heptane, octane-iso, 1,2, the solubleness in the 4-trimethyl-cyclohexane, and after stirring in 2 hours, represent, sees Table 1 by the maximum weight percentage composition of institute's energy dissolving resin with resin and solvent for solubleness.As shown in Table 1, the boiling point of normal heptane and octane-iso is lower, helps the separation of final product, but they are less to the dissolving resin degree.
Table 1C
5/ C
9Solubleness under 25 ℃ of the copolymerized petroleum resins in the 100ml solvent
| Normal heptane | Octane-iso | 1,2, the 4-trimethyl-cyclohexane |
| 0.80g | 0.84g | 26.5g |
Realize organic solvent of the present invention, preferred trimethyl-cyclohexane or C
9The hydrogenation products of aromatic hydrocarbons---naphthenic oil, its major ingredient is trimethyl-cyclohexane.Hydrogenation solvent trimethyl-cyclohexane or naphthenic oil can adopt following method preparation: adopt the JH-1 type to carry nickel Al
2O
3Carried catalyst is at 200 ℃ of temperature, pressure 2.0MPa, air speed 0.5～1h
-1, hydrogen-oil ratio 150～300: under 1 the condition, with the C of sym-trimethylbenzene, unsym-trimethyl benzene or reformation
9BTX aromatics is that raw material carries out hydrogenation reaction, generates corresponding trimethyl-cyclohexane or naphthenic oil.For example, with the sym-trimethylbenzene be raw material, hydrogenation under these conditions, transformation efficiency is 100%, and through mass spectroscopy, molecular weight of product is 126.24, be 1,3, the 5-trimethyl-cyclohexane, have 1,3,5-trimethylammonium (1 α, 3 α, 5 α) hexanaphthene and 1,3, two kinds of steric isomers of 5-trimethylammonium (1 α, 3 α, 5 β) hexanaphthene.With the unsym-trimethyl benzene is raw material, hydrogenation under these conditions, and transformation efficiency is 100%, through mass spectroscopy, molecular weight of product is 126.24, is 1,2, the 4-trimethyl-cyclohexane has 1,2,4-trimethylammonium (1 α, 2 β, 4 α) hexanaphthene and 1,2,4-trimethylammonium (1 α, 2 β, 4 β) two kinds of steric isomers of hexanaphthene.With the C that reforms
9BTX aromatics is a raw material, generates the naphthenic oil that corresponding major ingredient is a trimethyl-cyclohexane equally.
The hydrogenation solvent that makes as stated above---trimethyl-cyclohexane or naphthenic oil is to C
5/ C
9Copolymerized petroleum resin solubleness is bigger, and raises and increase rapidly with temperature, and the variation of its solubility with temperature sees Table 2.See from solubility property and obviously to be better than normal heptane and octane-iso equal solvent.Adopt naphthenic oil to make solvent, the concentration of resin solution is 10%～50% (wt%).
Table 2C
5/ C
9The solubleness of copolymerized petroleum resin in 100ml hydrogenation solvent
| 10℃ | 20℃ | 25℃ | 35℃ | 45℃ | 60℃ |
| 18.4g | 20.4g | 26.5g | 38.0g | 49.6g | 61.2g |
Because C
5/ C
9There are Unstable Substance and coloring matters such as unsaturated hydrocarbons, sulfide, colloid and bituminous matter in the copolymerized petroleum resin, before carrying out hydrogenation reaction, earlier remove wherein part objectionable impurities, help the quality of the hydrogenation resin of the carrying out of hydrogenation reaction and gained with sorbent material.Decolouring can be used has bigger specific surface area and pore volume, have special adsorptive power and ion-exchange performance, thereby the processing of decolouring of stronger decoloring ability and active sorbent material is arranged, such as the partial impurities of removing with atlapulgite or macroporous adsorbent resin etc. in the resin solution, the capable again hydrotreatment of the resin solution after the decolouring.
In existing hydrogenation of petroleum resin technology, used catalyzer is precious metal or other complicated catalyst systems, costs an arm and a leg or the preparation process complexity.In the present invention, hydrogenation catalyst be hydrogenation reaction use always nickel catalyst carried, as JH-1 type catalyzer.Described catalyst n i content is 35%～50% (wt%), and carrier is γ-Al
2O
3, specific surface is 150～300m
2/ g, bulk density 0.9～1.1kg/L, pore volume are 0.2～0.4ml/g, radial crushing strength 〉=130N/cm.Catalyzer adopts immersion process for preparing commonly known in the art, with γ-Al
2O
3Pour in the nickel nitrate solution, flooded 4-5 hour, after the mixture ageing drying, get hydrogenation catalyst through high-temperature roasting.Resulting catalyzer is two pore size distributions that disperse, and small aperture is about 30_, and macropore diameter is about 80_.
Hydrogenation C produced according to the present invention
5/ C
9Copolymerized petroleum resin, hydrogenation reaction adopt fixed-bed reactor to carry out, and reaction conditions is: 220～270 ℃ of temperature of reaction, pressure 2.0～8.0MPa, volume space velocity 0.1～1.0h
-1, hydrogen-oil ratio 300～3000: 1.But improve the temperature of reaction fast reaction speed, promote hydrogenation reaction, reduce foreign matter content, but the too high meeting of temperature causes the degraded side reaction, and accelerate the carbon deposit on the catalyzer, in the work-ing life of having reduced catalyzer, the preferable range of temperature of reaction is 230～260 ℃.Pressurize can improve speed of response, help raw material and spread on catalyzer, but pressurize can increase the consumption of facility investment and energy consumption, and the preferable range of reaction pressure is 2.0～5.0MPa.Reducing air speed can increase the duration of contact of raw material and catalyzer, increases the hydrogenation degree of depth, helps removing impurity, but air speed is low excessively, and stock oil residence time in reactor prolongs, and the growing amount of coke increases, can shorten the work-ing life of catalyzer, the preferred 0.375～0.5h of volume space velocity
-1Improve hydrogen-oil ratio, hydrogenation rate improves (bromine number reduction), the hydrogenation of resin is effective, this is owing to improve the hydrogen dividing potential drop, the cause that helps hydrogenation reaction, but excessive hydrogen-oil ratio influences the treatment capacity of petroleum resin and increases energy consumption, is unfavorable for improving plant efficiency, and the scope of the preferred hydrogen-oil ratio of the present invention is 600: 1～900: 1.
Hydrogenation afterreaction product promptly gets hydrogenation C after reclaiming solvent
5/ C
9Copolymerized petroleum resin.Reclaim solvent, can adopt the method for underpressure distillation commonly used, recovered solvent can be recycled.
Beneficial effect
According to the inventive method to C
5/ C
9Copolymerized petroleum resin hydrogenation preparing hydrogenation C
5/ C
9Copolymerized petroleum resin can make that look shallow, flavor is low, softening temperature is higher, the hydrogenation C that bromine number is low, ageing-resistant
5/ C
9Copolymerized petroleum resin.Resulting hydrogenation C
5/ C
9Copolymerized petroleum resin, its colourity is less than 3
#, softening temperature is more than 85 ℃, and bromine valency and thermostability index etc. all is significantly increased, and the product quality excellence can satisfy the demand of fields such as hot melt adhesive, hot melt road marking paint and extraordinary tackiness agent to petroleum resin, has enlarged C
5/ C
9The range of application of copolymerized petroleum resin.In preferred version of the present invention, can make softening temperature＞90 ℃, form and aspect 1
#Hydrogenated petroleum resin.
The method according to this invention, adopt general nickel catalyst carried, low price, and hydrogenation conditions gentleness, reaction process is steady, easy to control.
According to the present invention, with the C of Jingjiang City chemical industry company limited of Huiyuan (former Jingjiang solvent factory)
5/ C
9Copolymerized petroleum resin carries out hydrogenation reaction (concrete reaction conditions and reaction process see embodiment 1), obtains softening temperature＞90 ℃, form and aspect 1
#And the bromine valency is less than 2gBr
2The water white hydrogenated petroleum resin of/100g.C
5/ C
9Performance index relatively sees Table 3 before and after the copolymerized petroleum resin hydrogenation.
Table 3C
5/ C
9The comparison of index before and after the copolymerized petroleum resin hydrogenation
| Analysis project | Analytical procedure | Hydrogenating materials not | The hydrogenation effect |
| Softening temperature, ℃ | GB2294-92 | 122 | ＞90 |
| The bromine valency, g Br 2/100g | HG2231-91 | 65.1 | ＜2 |
| Form and aspect (Fe-Co method) (sample: toluene=1: 1) | GB12007.1 | 11 # | 1 # |
| Stability | GB12007.1 | ＜5 # | |
| Acid number, mg KOH/g | GB2895 | 0.24 | 0 |
| Ash content, % | GB2295 | 0.02 | 0.02 |
| Color | Range estimation | Brown | Water white |
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not exceeded with embodiment, but is limited by the scope of claim.
Embodiment
In each following embodiment, the testing method of each index is as follows:
Form and aspect: iron-cobalt colorimetry, i.e. Gardner method (GB12007.1-89, resin are made into 50% toluene solution and iron-cobalt color solution colorimetric)
Softening temperature: ring and ball method (GB/T 2294-1997).
Bromine number: volumetry (HG 2231-91)
Thermostability: petroleum resin are in 175 ℃ of following constant temperature resulting form and aspect (iron-cobalt colorimetry) after 5 hours
Acid number: GB264-83
The C that is adopted
5/ C
9Copolymerized petroleum resin raw material (from chemical industry company limited of Jingjiang City Huiyuan) index is as follows:
Softening temperature, ℃ 122
Form and aspect,
#11
Bromine number, g Br
2/ 100g 65.1
Acid number, mg KOH/g 0.24
Ash content, % 0.02
The color brown
In following embodiment, the subscript * in the embodiment sequence number represents this example not within the scope that the present invention protected, the subscript in the form and aspect index value+or-its colourity of expression is dark slightly or shallow slightly than reference colour.
Embodiment 1
In the present embodiment, the hydrogenation reaction device is that loaded catalyst is the small-sized gas-liquid-solid medium-pressure hydrocracking reaction unit of 40ml, select 1Cr18Ni9Ti fixed-bed reactor, three sections temperature control Reaktionsofens, integral type preheating mixer for use, design pressure 10Mpa installs actual temperature-controlled precision＜1 ℃.Gas feed adopts the metering of gas mass flow amount controller, and tail gas adopts wet flow indicator metering, gas raw material flow control scope: 0～500ml/min (MAX).The liquid reactions material uses the metering of double plunger volume pump, liquid flow rate span of control: 0.1～100ml/h (MAX).Pressure detection applying pressure transmitter connects digital wash, and the intelligent control digital display meter is selected in temperature control, detection for use.
Hydrogenation catalyst adopts the JH-1 type to carry nickel Al
2O
3Carried catalyst, wherein Ni content is 40% (wt%), specific surface is 220m
2/ g, bulk density 1.0kg/L, pore volume are 0.22ml/g, and radial crushing strength 180N/cm, catalyzer are two pore size distributions that disperse, and small aperture is about 30_, and macropore diameter is about 80_.Catalyzer is that 2.0MPa, temperature are 400 ℃, H at pressure
2Flow is under the condition of 100ml/min, activation 48h.
With raw material C
5/ C
9Copolymerized petroleum resin is dissolved in (1,2, the 4-trimethyl-cyclohexane) in the resulting naphthenic oil of unsym-trimethyl benzene hydrogenation, C
5/ C
9Copolymerized petroleum resin concentration is 20% (wt%), adds activated decoloration, decolouring back elimination atlapulgite.Hydrogen is regulated control and is measured flow by mass flow controller behind the decompression pressure regulating valve, enters preheating (vaporization) mixing tank.After petroleum resin solution after the decolouring was carried by volume pump and regulated flow, preheating (vaporization) and mix with hydrogen in preheating (vaporization) mixing tank entered the reactor catalyst bed, carries out catalytic hydrogenation reaction continuously.The hydrogenation reaction processing condition are: temperature is that 250～260 ℃, pressure are that 3.0MPa, air speed are 0.5h
-1, hydrogen-oil ratio is 600: 1.Reacted high temperature hydrogenation product enters the condenser cooling after filtering through filter, and cooling back gas-liquid mixture carries out gas-liquid separation through the high-pressure gas-liquid separating tank.Gas-phase product metering back is from drain emptying, and liquid product enters holding tank through collection.Steam the hydrogenation solvent under hydrogenation products in the holding tank reduced pressure for recycling in rotatory evaporator, hydrogenation products promptly obtains hydrogenation C after reclaiming solvent
5/ C
9Copolymerized petroleum resin, recovered solvent can be recycled.
Carry out C according to present embodiment
5/ C
9The copolymerized petroleum resin hydrogenation reaction obtains softening temperature＞90 ℃, form and aspect 1
#And the bromine valency is less than 2g Br
2The water white hydrogenated petroleum resin of/100g.
Embodiment 2～8
Embodiment 2～8 realizes the present invention under different hydrogenation reaction temperature, and temperature of reaction is carried out preferably.
Specific implementation process is selected the JH-1 catalyzer among the embodiment 1 for use with embodiment 1, catalyst volume 40ml, material concentration 20%, hydrogenation reaction pressure 3.0MPa, air speed 0.5h
-1, hydrogen-oil ratio 600: 1.Change the hydrogenation reaction temperature in 190～280 ℃ of scopes, resulting hydrogenated petroleum resin is as shown in table 4.
The influence of table 4 temperature of reaction
| Embodiment | 2 | 3 | 4 | 5 | 6 | 7 | 8 * |
| Temperature of reaction, ℃ | 190 | 220 | 230 | 250 | 260 | 270 | 280 |
| Form and aspect, # | 5 | 3 | 1 | 1 | 1 | 1 - | 1 - |
| Softening temperature, ℃ | 100 | 98 | 98 | 96 | 92 | 90 | 82 |
| Hydrogenation rate, % | 95.2 | 97.9 | 98.6 | 98.6 | 98.8 | 98.9 | 98.9 |
But improve the temperature of reaction fast reaction speed, promote hydrogenation reaction, reduce foreign matter content, but the too high meeting of temperature causes the degraded side reaction, and accelerate the carbon deposit on the catalyzer, the work-ing life of having reduced catalyzer.Along with the rising of temperature of reaction, the resin look behind the hydrogenation reduces number gradually, and when temperature is brought up to after 230 ℃, it is very slow that look number lowers.The softening temperature of resin reduces along with the rising of temperature of reaction, and this is because the raising of temperature has increased the degraded side reaction, thereby has reduced softening temperature.Hydrogenation rate raises with the rising of temperature of reaction.The preferable range of temperature of reaction of the present invention is 230～260 ℃.
Embodiment 9～13
Embodiment 9～13 realizes the present invention under different hydrogenation reaction pressure, and reaction pressure is carried out preferably.
Specific implementation process is selected the JH-1 catalyzer among the embodiment 1 for use with embodiment 1, catalyst volume 40ml, and material concentration 20%, the hydrogenation reaction temperature is 250 ℃, air speed 0.5h
-1, hydrogen-oil ratio 600: 1.Change hydrogenation reaction pressure in the scope of 1.0～6.0MPa, resulting hydrogenated petroleum resin is as shown in table 5.
The influence of table 5 reaction pressure
| Embodiment | 9 * | 10 | 11 | 12 | 13 |
| Reaction pressure, MPa | 1.0 | 2.0 | 4.0 | 5.0 | 6.0 |
| Form and aspect, # | 5 | 1 + | 1 | 1 | 1 - |
| Softening temperature, ℃ | 82 | 95 | 98 | 98 | 100 |
By table 5 finding, pressurize can improve speed of response, helping raw material spreads on catalyzer, but pressurize can increase the consumption of facility investment and energy consumption, considers the hydrogenation degree of depth from energy-conservation aspect, reduces the form and aspect number of resin, improve softening temperature, and remove impurity, and suppressing coking, preferred pressure scope of the present invention is 2.0～5.0MPa.
Embodiment 14～18
Embodiment 14～18 realizes the present invention under different volume space velocities, and volume space velocity is carried out preferably.
Volume space velocity: the volume number that refers to pass through on the per volume of catalyst in the unit time stock liquid.
Specific implementation process is selected the JH-1 catalyzer among the embodiment 1 for use with embodiment 1, catalyst volume 40ml, and material concentration 20%, the hydrogenation reaction temperature is 250 ℃, pressure 3.0MPa, hydrogen-oil ratio 600: 1.At 0.25～1.0h
-1Scope in change volume space velocity, resulting hydrogenated petroleum resin is as shown in table 6.
The influence of table 6 reaction velocity
| Embodiment | 14 | 15 | 16 | 17 | 18 |
| Air speed, h -1 | 0.25 | 0.375 | 0.5 | 0.75 | 1 |
| Form and aspect, # | 1- | 1 | 1 | 2 | 3 |
| Softening temperature, ℃ | 98 | 97 | 98 | 95 | 89 |
| Hydrogenation rate, % | 98.9 | 98.9 | 98.8 | 98.3 | 97.5 |
As can be seen from Table 6, along with air speed improves, the form and aspect variation of resin, softening temperature reduce, bromine number increases (hydrogenation rate reduction), the hydrogenation effect has been described worse and worse, and reduces the duration of contact that air speed means increases raw material and catalyzer, increase the hydrogenation degree of depth, helped removing impurity.But air speed is low excessively, has not only reduced the treatment capacity of device, and stock oil residence time in reactor prolongs the growing amount increase of coke, thereby the work-ing life of shortening catalyzer.Take all factors into consideration, the preferred air speed scope of the present invention is 0.375～0.5h
-1
The air speed of hydrogenation of petroleum resin is generally lower, can explain with the steric hindrance diffusion notion that Pappenheimer nineteen fifty-three proposes, when to be molecular diameter with the ratio in catalyzer aperture be 0.07-0.60, reactant and product were more much smaller than the velocity of diffusion under the original capacity condition of divergence in full of liquid hole internal diffusion speed.People such as Satterfield showed with non-reaction conditions experiment that molecular diameter was with the ratio in aperture in 1973 at 0.2 o'clock, and velocity of diffusion is a controlled step, and reaction can only be carried out on catalyst surface.Estimation is the result show, the ratio in petroleum resin molecular diameter and catalyzer aperture is much larger than 0.2.Therefore,, the dispersity of active ingredient can be increased on the one hand, the catalyzer aperture can be strengthened on the other hand at the catalyzer outside surface in order to improve hydrogenation reaction speed.
Embodiment 19～23
Embodiment 19～23 realizes the present invention under different hydrogen-oil ratio conditions, and hydrogen-oil ratio is carried out preferably.
Hydrogen-oil ratio: refer in the unit time by the hydrogen of beds and the ratio of raw material volume, i.e. both throughput ratios.
Specific implementation process is selected the JH-1 catalyzer among the embodiment 1 for use with embodiment 1, catalyst volume 40ml, and material concentration 20%, the hydrogenation reaction temperature is 250 ℃, pressure 3.0MPa, air speed 0.5h
-1Change hydrogen-oil ratio in 150: 1～1200: 1 scope, resulting hydrogenated petroleum resin is as shown in table 7
The influence of table 7 hydrogen-oil ratio
| Embodiment | 19 * | 20 | 21 | 22 | 23 |
| Hydrogen-oil ratio | 150∶1 | 300∶1 | 600∶1 | 900∶1 | 1200∶1 |
| Form and aspect, # | 5 | 2 | 1 | 1- | 1 - |
| Hydrogenation rate, % | 96.7 | 97.9 | 98.8 | 98.9 | 98.9 |
As can be seen from Table 7, along with the raising of hydrogen-oil ratio, hydrogenation rate improves (bromine number reduction), and the hydrogenation effect of resin is become better and better, and this is owing to improve the hydrogen dividing potential drop, helps the cause of hydrogenation reaction.But excessive hydrogen-oil ratio influences the treatment capacity of petroleum resin and increases energy consumption, is unfavorable for improving plant efficiency.The hydrogen-oil ratio that hydrogenation process adopts is all big than chemical depletion amount, and major cause is as follows:
(1) there are enough hydrogen dividing potential drops in maintenance system, makes reaction be easy to carry out, and guarantees quality product;
(2) excessive hydrogen can play the guard catalyst surface, reduces the condensation coking of hydrogenation material at catalyst surface to a certain extent, keeps the stability of catalyzer and increases the service life.
(3) a large amount of hydrogen help the quiet run temperature, make the easier control of temperature of reaction.
According to the result of above-mentioned analysis and test, the scope of the preferred hydrogen-oil ratio of the present invention is 600: 1～900: 1.
Embodiment 24～26
Embodiment 24～26 uses different nickel catalyst carried realization the present invention, and support of the catalyst is γ-Al
2O
3
Specific implementation process is with embodiment 1, and different catalysts catalyst system therefor volume is 40ml, material concentration 20%, and hydrogenation conditions is: temperature of reaction is 250 ℃, pressure 3.0MPa, air speed 0.5h
-1, hydrogen-oil ratio 600: 1, resulting hydrogenated petroleum resin is as shown in table 8.
The influence of table 8 catalyzer
| Embodiment | 24 | 25 | 26 |
| Catalyzer | JH-2 | JH-1 | JH-3 |
| Ni content, wt% | 35 | 40 | 45 |
| Specific surface, m 2/g | 252 | 220 | 208 |
| Pore volume, ml/g | 0.20 | 0.22 | 0.27 |
| Form and aspect, # | 1 | 1 - | 1 - |
| Hydrogenation rate, % | 96.7 | 98.9 | 98.9 |
The nickel catalyzator that uses in the experiment is with γ-Al
2O
3Be carrier, Ni content is at 35%～50% (wt%), and specific surface is at 150～300m
2/ g, pore volume are 0.2～0.4ml/g, and catalyzer is two pore size distributions that disperse, and small aperture is about 30_, and macropore diameter is about 80_.In the table 8, list three kinds of nickel catalyzators of preparation, be used to prepare hydrogenation C
5/ C
9Copolymerized petroleum resin, form and aspect have reached the purpose to copolymerized petroleum resin deodorizing, decolouring, increase stability all smaller or equal to No. 1.
Claims (9)
1, a kind of hydrogenation C
5/ C
9The preparation method of copolymerized petroleum resin is with C
5/ C
9Copolymerized petroleum resin is dissolved in the organic solvent, adds the sorbent material decolouring, and resin solution after the decolouring and hydrogen enter and carries out catalytic hydrogenation reaction in the fixed-bed reactor, 220～270 ℃ of temperature of reaction, pressure 2.0～8.0MPa, volume space velocity 0.1～1.0h
-1, hydrogen-oil ratio 300～3000: 1; Hydrogenation catalyst adopts nickel catalyst carried, and Ni content is weight percentage 35%～50%, and carrier is γ-Al
2O
3, specific surface is 150～300m
2/ g, pore volume are 0.2～0.4ml/g; Hydrogenation afterreaction product promptly gets hydrogenation C after reclaiming solvent
5/ C
9Copolymerized petroleum resin.
2, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described organic solvent is normal heptane, octane-iso or trimethyl-cyclohexane.
3, hydrogenation C according to claim 2
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described organic solvent is a trimethyl-cyclohexane, and the weight percent concentration of resin solution is 10%～50%.
4, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described sorbent material is atlapulgite or macroporous adsorbent resin.
5, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described hydrogenation reaction temperature is 230～260 ℃.
6, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described hydrogenation reaction pressure is 2.0～5.0MPa.
7, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described hydrogenation reaction volume space velocity is 0.375～0.5h
-1
8, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that described hydrogenation reaction hydrogen-oil ratio is 600: 1～900: 1.
9, hydrogenation C according to claim 1
5/ C
9The preparation method of copolymerized petroleum resin is characterized in that reclaiming solvent and adopts vacuum distillation method.
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