CN102924659A - Preparation method for C9 hydrogenation petroleum resin - Google Patents

Preparation method for C9 hydrogenation petroleum resin Download PDF

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CN102924659A
CN102924659A CN2012104510841A CN201210451084A CN102924659A CN 102924659 A CN102924659 A CN 102924659A CN 2012104510841 A CN2012104510841 A CN 2012104510841A CN 201210451084 A CN201210451084 A CN 201210451084A CN 102924659 A CN102924659 A CN 102924659A
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hydrogenation
petroleum resin
catalyzer
reaction
catalyst
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段大勇
吴俊华
张立群
李洁
齐彦伟
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China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention relates to a preparation method for C9 hydrogenation petroleum resin. The C9 hydrogenation petroleum resin is dissolved in organic solvent, and the concentration of the C9 hydrogenation petroleum resin is 5wt %-30wt%. The C9 hydrogenation petroleum resin is filtered to remove undissolved substances, then subjected to a first section of hydrodesulfurization process and a second section of hydrogenation decoloration process, and finally subjected to the process of decompression rectification and solvent recovery to obtain C9 hydrogenation petroleum resin products. The preparation method adopts two-section hydrogenation, improves reaction activity, selectivity and impurity resistant capability, is wide in adaptability of C9 petroleum resin raw materials, and obtains C9 petroleum resin through adoption of thermal polymerization or catalytic polymerization. No matter impurity content in resin solution is high or low, particularly, when sulphur content is high in the resin solution, the two-step hydrogenation process can be carried out through the preparation method, and the C9 hydrogenation petroleum resin with high performance is obtained. Through the first section of hydrodesulfurization, hydrogenation noble metal catalyst in the second section is effectively protected. Service life of catalyst is greatly prolonged. Reaction pressure of the two-section hydrogenation is quite low, and industrial production cost is little.

Description

A kind of preparation method of C9 hydrogenated petroleum resin
Technical field
The present invention relates to petrochemical industry, is a kind of method of being produced the C9 hydrogenated petroleum resin by the C9 petroleum resin.
Background technology
Petroleum resin are that by product C5, C9 in the preparing ethylene by steam cracking process is as raw material, through thermopolymerization or catalyzed polymerization and a kind of thermoplastic resin that makes, have that light fastness is good, electrical insulating property is good, solvability good, with advantages such as the consistencies such as natural resin, synthetic resins, softening agent are good, has widely application at aspects such as coating, extraordinary tackiness agent, printing ink.
Hydrogenation of petroleum resin makes two keys and the part phenyl ring in the petroleum resin be able to saturated, deviate from again resin residual halogen element in polymerization process, improve colourity, photo and thermal stability, oxidation stability and the ultraviolet resistance of resin, improved product matter scape, expanded purposes.Development along with tackiness agent and sealing agent application, particularly the application of transparent pressure sensitive adhesive tape, outdoor seal gum, disposable sanitary articles, medical adhesive tape, traffic paint and polyolefin modifiers all needs the petroleum resin of lighter color, odorless and good stability, market is very fast to the demand growth of hydrogenated petroleum resin thus, has also promoted the development of Hydrogenation Technology of Petroleum Resin.
The hydrogenation of petroleum resin catalyzer has the powdery nickel catalyzator according to the technique difference, and load type palladium, platinum and nickel catalyzator are also arranged.Fixed bed hydrogenation technique all adopts loaded catalyst, and support of the catalyst generally is aluminum oxide and diatomite.The supported nickel catalyst use temperature is lower, and generally about 260 ℃, the nickel massfraction is 40~60%.The catalyzer of supported palladium, palladium content be at 0.5~2.O%, 280~290 ℃ of temperature of reaction.External many companies adopt palladium catalyst at present, and it can limit adding hydrogen into resin degraded side reaction effectively.The adding hydrogen into resin catalyzer is made with nickel, the tungsten of sulphided state by the company that also has, although it has higher activity to adding hydrogen into resin, the hydrogenation degraded is more serious, and the final resin yield only has about 80%, and softening temperature drops to 9O ℃ from 120 ℃.Catalyzer is the key of hydrogenated petroleum resin technology, and the developing direction of hydrogenation of petroleum resin catalyzer is improve catalyzer active and stable from now on, reduces side reaction and suitably reduces manufacturing cost.
With the year by year raising in China's cracking ethylene throughput, the quantity of pyrolysis c9 cut also constantly increases, the domestic C9 petroleum resin that generally are prepared as, but because the pyrolysis c9 feed composition is many, the color of resin of producing is generally darker, be brown or brown, thermostability is relatively poor, thereby has limited range of application.Domestic still being at present laboratory stage aspect the C9 hydrogenation of petroleum resin, not yet form industrially scalable.
Chinese patent CN1084521A has introduced a kind of method of hydrotreating of high raw material petroleum resin, the dissolution with solvents C9 petroleum resin that get with C9 arenes catalytic Hydrogenation, resin concentration is 30~70% (weights), shortening on fixed bed, hydrogenation reaction pressure is 3.0~20MPa, temperature is 240~320 ℃, and weight space velocity is 0.1~1.5h -1Hydrogenation catalyst is to carry nickel or carried palladium catalyst, and carrier is aluminium sesquioxide and diatomite.
Chinese patent CN1199742A discloses the method for hydrotreating of a kind of C5 or C9 petroleum resin, be petroleum resin are dissolved in the solvent, under the condition of 220~350 ℃ of hydrogen pressure 2~15MPa, temperature of reaction, with prevulcanized NiO-WO 3-MgO/Al 2O 3Catalyzer contact, Separation and Recovery product then, solvent cycle is used.This catalyzer consists of 1.0~10.0%NiO, 15~32%WO 3, 0.2~3.5% MgO and balance carriers aluminum oxide, its specific surface area is 120~250m 2/ g, pore volume are 0.4~0.9ml/g.
The method that Chinese patent CN18033871A discloses the decolouring of a kind of C5 and C9 petroleum resin autoclave shortening, eliminated the unusual smell, the method with modified raney ni as catalyzer, in the autoclave high-pressure reactor, put into petroleum resin, solvent and catalyzer, catalyst levels is 1~20wt% of petroleum resin, temperature of reaction is 100~250 ℃, reaction system pressure is 1.0~10MPa, keeps 2~10 hours reaction times.
Chinese patent CN101967214A discloses a kind of method by thick C 9 petroleum resin production hydrogenated carbon 9 petroleum resin, that the thick C 9 petroleum resin that obtains of the C 9 fraction polymerization take the cracking of ethylene by-product is as raw material, through dissolution with solvents, standing sedimentation, then carry out respectively Hydrogenation and process; Supernatant liquid adopts the fixed bed Hydrogenation, and catalyzer consists of the NiO of 2~10 heavy %, the WO of 10~25 heavy % 3, 1~5 heavy % MoO 3, 5~10 heavy % CuO, surplus is alumina supporter, its specific surface area is 100~250m 2/ g, pore volume are 0.3~1.0ml/g.The upper strata resin clear liquid of 40~60 heavy % is by contacting with the loaded catalyst that contains Ni, W and Mo of prevulcanized, and reaction pressure is 8.0~20.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 0.5~2h -1; The turbid liquid of lower floor adopts reaction autoclave shortening, and catalyzer consists of the NiO of 5~15 heavy %, the WO of 10~25 heavy % 3, 1~5 heavy % MoO 3, 5~10 heavy % ZnO, surplus is alumina supporter, its specific surface area is 100~250m 2/ g, pore volume are 0.4~0.8ml/g.By contacting hydrogenation with the loaded catalyst that contains Ni, W and Zn of prevulcanized, reaction pressure is 6.0~12.0MPa in reactor, and temperature of reaction is 200~300 ℃, 4~12 hours reaction times.
Used hydrogenation catalyst all adopts single stage method to prepare the C9 hydrogenated petroleum resin in above-mentioned these patents, but because present development along with C9 petroleum resin polymerization technique, the yield of thick C9 petroleum resin and output have significantly growth, meanwhile bring foreign matter content height in the petroleum resin, sulphur, nitrogen content height, the increase of especially insoluble sol content, the life-span that to cause above-mentioned patent weak point be catalyzer does not reach industrial requirements, and product colour is also treated further improvement.
Summary of the invention
The object of the invention is to provide a kind of preparation method of C9 hydrogenated petroleum resin, the method can make that colourity is good, the bromine valency is low, the C9 hydrogenated petroleum resin of Heat stability is good, can under lower reaction pressure, react again, and catalyst life is greatly improved.
Technical scheme of the present invention is as follows:
A kind of preparation method of C9 hydrogenated petroleum resin is dissolved in the C9 petroleum resin in the organic solvent, and C9 petroleum resin concentration is 5~30wt%; Remove after filtration insolubles, process through the decolouring of one-stage hydrogenation desulfurization, secondary hydrogenation again, again after solvent is reclaimed in rectification under vacuum, obtain C9 hydrogenated petroleum resin product at last.
The catalyzer of described one-stage hydrogenation desulfurization is the loaded catalyst of nickel content 10~40wt%, and carrier is that specific surface area is 100~250m 2/ g modified aluminas, pore volume are 0.3~1.0ml/g; C9 petroleum resin solution after the filtration contacts with catalyzer, and hydrogenation reaction pressure is 2.0~6.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 1~5h -1
Described secondary hydrogenation decolouring catalyzer is the loaded catalyst that contains Pd 0.1~2wt% and contain Pt 0.1~2wt%, and carrier is that specific surface area is 100~250m 2/ g, pore volume are the modified aluminas of 0.3~1.0ml/g; C9 petroleum resin solution after the one-stage hydrogenation desulfurization contacts with catalyzer, and hydrogenation reaction pressure is 6.0~12.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 1~5h -1Adopt the fixed bed Hydrogenation to process.
Carrier in described one-stage hydrogenation desulfurization catalyst and the secondary hydrogenation decolouring catalyzer is modified aluminas, to make with pseudo-boehmite, aluminium hydroxide, the former powder of diatomite and organic expanding agent, wherein by percentage to the quality, the pseudo-boehmite proportion is 20~80%, the aluminium hydroxide proportion is 10~40%, the former powder proportion of diatomite is 10~40%, and organic expanding agent proportion is 2~10%.
Described organic solvent is one or more of saturated alkane of C6~C10.
Described one-stage hydrogenation desulfurization catalyst is the loaded catalyst of nickel content 20~30wt%.
C9 petroleum resin solution after the described filtration contacts with catalyzer, adopts fixed bed low pressure catalytic hydroprocessing, and hydrogenation reaction pressure is 2.0~6.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 1~5h -1
Described secondary hydrogenation decolouring catalyzer contains the loaded catalyst of Pt 0.3~1wt% for containing Pd 0.3~1wt%.
C9 petroleum resin solution after the one-stage hydrogenation desulfurization contacts with catalyzer, adopts the fixed bed Hydrogenation to process, and hydrogenation reaction pressure is 6.0~12.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 1~5h -1
Carrier in above-mentioned one-stage hydrogenation desulfurization catalyst and the secondary hydrogenation decolouring catalyzer is modified aluminas, is to make by kneading, moulding, drying, roasting with pseudo-boehmite, aluminium hydroxide, the former powder of diatomite and organic expanding agent; With above-mentioned carrier impregnation metal salt solution, dry, roasting; In reactor, use hydrogen reducing before using;
The concentration that the C9 petroleum resin are dissolved in the organic solvent is 5~30wt%.
According to the method described in the present invention, its preferred version is characterised in that:
The C9 petroleum resin are dissolved in the organic solvent, remove after filtration insolubles, process through the decolouring of one-stage hydrogenation desulfurization, secondary hydrogenation again, again after solvent is reclaimed in rectification under vacuum, obtain C9 hydrogenated petroleum resin product at last;
The one-stage hydrogenation desulfurization catalyst is the loaded catalyst of nickel content 20~30wt%, and carrier is modified aluminas; C9 petroleum resin solution after the filtration contacts with catalyzer, adopts fixed bed low pressure catalytic hydroprocessing, and hydrogenation reaction pressure is 3.0~5.0MPa, and temperature of reaction is 280~320 ℃, and the liquid air speed is 2~4h -1
Secondary hydrogenation decolouring catalyzer is the loaded catalyst that contains Pd 0.3~1wt% and contain Pt 0.3~1wt%, and carrier is modified aluminas; C9 petroleum resin solution after the one-stage hydrogenation desulfurization contacts with catalyzer, adopts the fixed bed Hydrogenation to process, and hydrogenation reaction pressure is 8.0~10.0MPa, and temperature of reaction is 280~320 ℃, and the liquid air speed is 2~4h -1
Carrier in above-mentioned one-stage hydrogenation desulfurization catalyst and the secondary hydrogenation decolouring catalyzer is modified aluminas, to make by kneading, moulding, drying, roasting with pseudo-boehmite, aluminium hydroxide, the former powder of diatomite and organic expanding agent, wherein the pseudo-boehmite proportion is 20~80%, the aluminium hydroxide proportion is 10~40%, the former powder proportion of diatomite is 10~40%, and organic expanding agent proportion is 2~10%.With above-mentioned carrier impregnation metal salt solution, drier, roasting; In reactor, use hydrogen reducing before using;
Described C9 petroleum resin refer to by thermopolymerization or the resulting petroleum resin of catalyzed polymerization C 9 fraction of cracking; Described organic solvent is selected from one or more in normal heptane, normal hexane, hexanaphthene, methylcyclohexane, the octane; The concentration that the C9 petroleum resin are dissolved in the organic solvent is 10~20wt%.
The petroleum resin raw material that the present invention was suitable for is by alkene or the resulting petroleum resin of diolefine such as dicyclopentadiene, vinylbenzene, vinyl toluene and indenes in thermopolymerization or the catalyzed polymerization C 9 fraction of cracking.When carrying out hydrogenation reaction, petroleum resin are with the solution form charging in inert organic solvents.
Owing to have a large amount of undersaturated pair of keys in the high molecular of petroleum resin and the molecule thereof, therefore the pore structure of modified aluminas is vital on the impact of catalyst performance, the catalyzer of the present invention's preparation should have the pore volume of requirement, its median pore diameter should be enough large, but avoid influential to the intensity of catalyzer.
The Separation and Recovery of product reaches through rectification under vacuum or wet distillation the hydrogenation after product with solvent recuperation.When reclaiming solvent, the still temperature of petroleum resin solution must not surpass 240 ℃, in order to avoid cause the cracking condensation of petroleum resin, and then cause the rise of petroleum resin color.
Owing to used the two-stage hydrogenation method, improved reactive behavior and selectivity and anti-impurity ability, thereby had following advantage in the method provided by the invention:
1. the inventive method is for the wide adaptability of C9 petroleum resin raw material, the C9 petroleum resin that adopt thermopolymerization or catalyzed polymerization to obtain, foreign matter content height in the resin solution no matter, when especially sulphur content is higher in the resin solution, all can adopt method provided by the invention to carry out two step hydrotreatments, obtain high performance C9 hydrogenated petroleum resin.
2. by the one-stage hydrogenation desulfurization, effectively protected the noble metal catalyst of secondary hydrogenation, catalyst life is greatly improved.
3. the reaction pressure of the present invention's two steps hydrogenation is relatively low, and industrial production cost is less.
Specific embodiment
Used C9 petroleum resin are the commercially available prod in the example, raw material properties such as following table 1:
Table 1.C9 petroleum resin raw material
Index C9-Ⅰ C9-Ⅱ
Softening temperature (℃) 116.5 120
Colourity, Gardner 10 9
The bromine valency, g bromine/100g oil 30.8 35.1
Thermostability >18 >18
Sulphur content (ppm) 366 285
C9-I petroleum resin are the C9 petroleum resin of catalyzed polymerization preparation in the table, and C9-II petroleum resin are the C9 petroleum resin of thermal polymerization method preparation.
1. the preparation of catalyzer:
Embodiment 1.
Take by weighing pseudo-boehmite 500g, aluminium hydroxide 200g, diatomite 300g and 100g polyoxyethylene glycol powder, mix, add 270g 6% diluted nitric acid aqueous solution and mediate, wore out 30 minutes under the room temperature, be shaped at banded extruder 3 strips in 120 ℃ of dryings 24 hours, in 800 ℃ of roastings 2 hours, obtain support of the catalyst afterwards, and crushing screening gets 10~20 order particles.Nickel nitrate solution with predetermined amount floods 10~20 order particles, prepares the catalyzer of four kinds of different Ni contents, and then through 120 ℃ of dryings, 420 ℃ of roastings namely got one-stage hydrogenation desulfurization catalyst precursor in the inventive method in 4 hours.In reactor, load 10ml before using, with 400 ℃ of lower reduction of hydrogen 3 hours.The catalyzer of listing different Ni contents in the following table 2 forms and physico-chemical parameter.
Table 2. the first step Hydrobon catalyst
Catalyst sample 1-1 1-2 1-3 1-4
Ni content (wt%) 10 20 30 40
Specific surface area (m 2/g) 128 125 130 126
Pore volume (ml/g) 0.58 0.58 0.57 0.55
Embodiment 2.
Take by weighing pseudo-boehmite 800g, aluminium hydroxide 100g, diatomite 100g and 50g polyoxyethylene glycol powder, mix, making nickel content according to the preparation method of embodiment 1 is 30% one-stage hydrogenation desulfurization catalyst precursor, and its specific surface area is 143m 2/ g, pore volume are 0.52ml/g.In reactor, load 10ml before using, with 400 ℃ of lower reduction of hydrogen 3 hours.Catalyzer is labeled as 2 #
Embodiment 3.
Take by weighing pseudo-boehmite 200g, aluminium hydroxide 400g, diatomite 400g and 80g polyoxyethylene glycol powder, mix, making nickel content according to the preparation method of embodiment 1 is 30% one-stage hydrogenation desulfurization catalyst precursor, and its specific surface area is 120m 2/ g, pore volume are 0.54ml/g.In reactor, load 10ml before using, with 400 ℃ of lower reduction of hydrogen 3 hours.Catalyzer is labeled as 3 #
Embodiment 4.
The carrier powder of preparation among the embodiment 1 is broken into 10~20 order particles, add the Palladous chloride of predetermined amount and the mixed aqueous solution of platinum chloride, flooded after 24 hours 120 ℃ of dryings 6 hours, again in 400 ℃ of roastings 4 hours, obtain the catalyzer of four kinds of different loads Pd and Pt content, in reactor, load 10ml before using, with 300 ℃ of lower reduction of hydrogen 3 hours.The catalyzer of listing different Pd and Pt content in the following table 3 forms and physico-chemical parameter.。
Table 3. secondary hydrogenation decolouring catalyzer
Catalyst sample 4-1 4-2 4-3 4-4
Pd content (wt%) 0.5 1 2 0.1
Pt content (wt%) 0.5 0.1 1 2
Specific surface area (m 2/g) 123 124 120 124
Pore volume (ml/g) 0.57 0.58 0.53 0.56
Embodiment 5.
The carrier powder of preparation among the embodiment 2 is broken into 10~20 order particles, add the Palladous chloride of predetermined amount and the mixed aqueous solution of platinum chloride, flooded after 24 hours 120 ℃ of dryings 6 hours, again in 400 ℃ of roastings 4 hours, obtain the catalyzer of load 0.5%Pd and 0.5%Pt, its specific surface area is 143m 2/ g, pore volume are 0.52ml/g.In reactor, load 10ml before using, with 300 ℃ of lower reduction of hydrogen 3 hours.Catalyzer is labeled as 5 #
Embodiment 6.
The carrier powder of preparation among the embodiment 3 is broken into 10~20 order particles, add the Palladous chloride of predetermined amount and the mixed aqueous solution of platinum chloride, flooded after 24 hours 120 ℃ of dryings 6 hours, again in 400 ℃ of roastings 4 hours, obtain the catalyzer of load 0.5%Pd and 0.5%Pt, its specific surface area is 120m 2/ g, pore volume are 0.54ml/g.In reactor, load 10ml before using, with 300 ℃ of lower reduction of hydrogen 3 hours.Catalyzer is labeled as 6 #
2.C9 petroleum resin the first step hydrogenating desulfurization:
Embodiment 7~12.
The catalyzer that embodiment 1,2,3 is obtained is used for embodiment 7~12, and the catalyzer of different Ni contents is screened.Test at fixed-bed reactor.Loaded catalyst is 10 milliliters, reaction pressure is adjusted to 3.0MPa, temperature maintains 300 ℃, reaction raw materials is the C9 petroleum resin/methylcyclohexane solution of 10% (weight), and the C9 petroleum resin are selected the C9-I of catalyzed polymerization preparation, and the liquid air speed is 4.0/h, hydrogen-oil ratio is 180, behind the reaction smooth running, sampling, bromine valency, colourity, the sulphur content of analytical reaction product solution.Test-results is listed in the table 4.
The screening of table 4. the first step hydrogenation catalyst
Figure BDA00002390508100061
But the result shows the most of two keys in the prepared catalyzer hydrogenation saturated resin, and removes the organosulfur in the resin, but color of resin do not shoal, and is substantially the same with the raw material color.
Embodiment 13~16.
The catalyzer 1-3 of embodiment 1 preparation is used for embodiment 13~16, investigates temperature of reaction to the impact of resin sweetening effectiveness.Test at fixed-bed reactor.Loaded catalyst is 10 milliliters, reaction pressure is adjusted to 3.0MPa, reaction raw materials is the C9 petroleum resin/methylcyclohexane solution of 10% (weight), the C9 petroleum resin are selected the C9-I of catalyzed polymerization preparation, and the liquid air speed is 4.0/h, and hydrogen-oil ratio is 180, change temperature of reaction, behind the smooth running, sampling, bromine valency, colourity, the sulphur content of analytical reaction product solution.Test-results is listed in the table 5.
The impact of table 5. one-stage hydrogenation temperature of reaction
Embodiment 17~20.
The catalyzer 1-3 of embodiment 1 preparation is used for embodiment 17~20, investigates reaction pressure to the impact of resin sweetening effectiveness.Test at the small fixed reactor.Loaded catalyst is 10 milliliters, temperature of reaction is 300 ℃, reaction raw materials is the C9 petroleum resin/methylcyclohexane solution of 10% (weight), the C9 petroleum resin are selected the C9-I of catalyzed polymerization preparation, and the liquid air speed is 4.0/h, and hydrogen-oil ratio is 180, change reaction pressure, behind the smooth running, sampling, bromine valency, colourity, the sulphur content of analytical reaction product solution.Test-results is listed in the table 6.
The impact of table 6. one-stage hydrogenation reaction pressure
Figure BDA00002390508100072
Embodiment 21~24.
The catalyzer 1-3 of embodiment 1 preparation is used for embodiment 21~24, investigates reaction liquid air speed, hydrogen-oil ratio to the impact of resin sweetening effectiveness.Test at the small fixed reactor.Loaded catalyst is 10 milliliters, reaction pressure 3.0MPa, temperature of reaction is 300 ℃, reaction raw materials is the C9 petroleum resin/methylcyclohexane solution of 10% (weight), and the C9 petroleum resin are selected the C9-I of catalyzed polymerization preparation, changes reaction feed speed and amounts of hydrogen, namely change reaction liquid air speed and hydrogen-oil ratio, behind the smooth running, sampling, bromine valency, colourity, the sulphur content of analytical reaction product solution.Test-results is listed in the table 7.
The impact of table 7. one-stage hydrogenation reaction liquid air speed and hydrogen-oil ratio
Figure BDA00002390508100073
Figure BDA00002390508100081
Embodiment 25~28.
The catalyzer 1-3 of embodiment 1 preparation is used for embodiment 25~28, investigates reaction raw materials type, reaction raw materials concentration and type of solvent to the impact of resin sweetening effectiveness.Test at the small fixed reactor.Loaded catalyst is 10 milliliters, and reaction pressure is adjusted to 3.0MPa, and temperature of reaction is 300 ℃, and the liquid air speed is 4.0/h, and hydrogen-oil ratio is 180, behind the smooth running, and sampling, bromine valency, colourity, the sulphur content of analytical reaction product solution.Test-results is listed in the table 8.
Table 8. one-stage hydrogenation raw material, solvent, concentration as influencing factor
Figure BDA00002390508100082
2.C9 petroleum resin secondary hydrogenation decolouring:
Raw material after the desulfurization of C9 petroleum resin one-stage hydrogenation is used for the secondary hydrogenation decolouring, and namely one-stage hydrogenation embodiment 7~24 products obtained therefroms mix, product bromine valency 2.48g/100g after mixing, colourity 4.1, sulphur content 2.23ng/ μ l.
Embodiment 29~34.
The secondary hydrogenation decolouring catalyzer that embodiment 4,5,6 is obtained is used for embodiment 29~34, and the catalyzer of different palladium platinum contents is screened.Test at fixed-bed reactor.Loaded catalyst is 10 milliliters, reaction pressure is adjusted to 8.0MPa, temperature maintains 320 ℃, reaction raw materials is the mixing prod after the one-stage hydrogenation desulfurization, the liquid air speed is 2.4/h, hydrogen-oil ratio is 300, and reaction product adopts rectification under vacuum to isolate solvent, and the results of performance analysis of gained resin product is listed in the table 9.
The catalyst screening of table 9. secondary hydrogenation
Figure BDA00002390508100091
Embodiment 35~38.
The secondary hydrogenation decolouring catalyzer 4-1 that embodiment 4 is obtained is used for embodiment 35~38, and reaction conditions is estimated.Test at the small fixed reactor.Loaded catalyst is 10 milliliters, reaction raw materials is the mixing prod after the one-stage hydrogenation desulfurization, change temperature of reaction, reaction pressure, liquid air speed and hydrogen-oil ratio, reaction product adopts rectification under vacuum to isolate solvent, and the results of performance analysis of gained resin product is listed in the table 10.
The contrast of table 10. secondary hydrogenation reaction conditions
Figure BDA00002390508100092
Embodiment 39~42.
The secondary hydrogenation decolouring catalyzer 4-1 that embodiment 4 is obtained is used for embodiment 39~42, tests at fixed-bed reactor.Loaded catalyst is 10 milliliters, reaction raw materials is each product after embodiment 25~28 one-stage hydrogenation desulfurization, reaction pressure is adjusted to 8.0MPa, temperature maintains 320 ℃, the liquid air speed is 2.4/h, hydrogen-oil ratio is 300, and reaction product adopts rectification under vacuum to isolate solvent, and the results of performance analysis of gained resin product is listed in the table 11.
Table 11. different material secondary hydrogenation comparing result
Figure BDA00002390508100101
Comparative Examples 1.
At the 4-1 catalyzer of fixed-bed reactor filling embodiment 4 preparations, loaded catalyst is 10 milliliters.Reaction raw materials directly uses the C9 petroleum resin of 10% (weight)/methylcyclohexane solution, the C9 petroleum resin are selected the C9-I of catalyzed polymerization preparation, reaction pressure is adjusted to 8.0MPa, and temperature maintains 320 ℃, and the liquid air speed is 2.4/h, hydrogen-oil ratio is 300, the reaction product color progressively rises, and reacts that color is faint yellow after 10 hours, adopts rectification under vacuum to isolate solvent, 106 ℃ of gained hydrogenation resin product softening temperatures, bromine valency 0.86gBr 2/ 100g oil, colourity (Gardner) is No. 4 looks.

Claims (10)

1. the preparation method of a C9 hydrogenated petroleum resin is characterized in that the C9 petroleum resin are dissolved in the organic solvent, and C9 petroleum resin concentration is 5~30wt%; Remove after filtration insolubles, process through the decolouring of one-stage hydrogenation desulfurization, secondary hydrogenation again, again after solvent is reclaimed in rectification under vacuum, obtain C9 hydrogenated petroleum resin product at last.
2. the method for claim 1, the catalyzer that it is characterized in that described one-stage hydrogenation desulfurization is the loaded catalyst of nickel content 10~40wt%, carrier is that specific surface area is 100~250m 2/ g modified aluminas, pore volume are 0.3~1.0ml/g; C9 petroleum resin solution after the filtration contacts with catalyzer, and hydrogenation reaction pressure is 2.0~6.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 1~5h -1
3. the method for claim 1 is characterized in that described secondary hydrogenation decolouring catalyzer is the loaded catalyst that contains Pd 0.1~2wt% and contain Pt 0.1~2wt%, and carrier is that specific surface area is 100~250m 2/ g, pore volume are the modified aluminas of 0.3~1.0ml/g; C9 petroleum resin solution after the one-stage hydrogenation desulfurization contacts with catalyzer, and hydrogenation reaction pressure is 6.0~12.0MPa, and temperature of reaction is 250~350 ℃, and the liquid air speed is 1~5h -1Adopt the fixed bed Hydrogenation to process.
4. method as claimed in claim 2 or claim 3, it is characterized in that the carrier in described one-stage hydrogenation desulfurization catalyst and the secondary hydrogenation decolouring catalyzer is modified aluminas, to make with pseudo-boehmite, aluminium hydroxide, the former powder of diatomite and organic expanding agent, wherein by percentage to the quality, the pseudo-boehmite proportion is 20~80%, the aluminium hydroxide proportion is 10~40%, and the former powder proportion of diatomite is 10~40%, and organic expanding agent proportion is 2~10%.
5. the method for claim 1 is characterized in that described organic solvent is one or more of saturated alkane of C6~C10.
6. method as claimed in claim 5 is characterized in that described organic solvent is selected from one or more in normal heptane, normal hexane, hexanaphthene, methylcyclohexane or the octane.
7. in accordance with the method for claim 1, it is characterized in that described one-stage hydrogenation desulfurization catalyst is the loaded catalyst of nickel content 20~30wt%.
8. in accordance with the method for claim 1, it is characterized in that the C9 petroleum resin solution after the described filtration contacts with catalyzer, adopt fixed bed low pressure catalytic hydroprocessing.
9. in accordance with the method for claim 1, it is characterized in that described secondary hydrogenation decolouring catalyzer for containing Pd 0.3~1wt%, contains the loaded catalyst of Pt 0.3~1wt%.
10. in accordance with the method for claim 1, it is characterized in that: the C9 petroleum resin solution after the one-stage hydrogenation desulfurization contacts with catalyzer, adopts the fixed bed Hydrogenation to process.
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CN103386302A (en) * 2013-07-25 2013-11-13 中国石油化工股份有限公司 Petroleum resin hydrogenation catalyst and preparation method thereof
CN104628956A (en) * 2013-11-08 2015-05-20 中国石油天然气股份有限公司 Preparation method of C9 petroleum resin
CN104710572A (en) * 2015-02-15 2015-06-17 广西大学 Method for modifying C9/C5 petroleum resin through hydrogenation-desulfuration coupling and equipment thereof
CN104877077A (en) * 2015-06-24 2015-09-02 大连理工大学 Method for preparing hydrogenated C9 petroleum resin
CN105585665A (en) * 2014-10-22 2016-05-18 中国石油化工股份有限公司 A method of preparing hydrogenated petroleum resin through continuous hydrogenation of petroleum resin
CN105664968A (en) * 2015-12-29 2016-06-15 广东工业大学 Catalyst for C9 petroleum resin hydrogenation reaction and preparation method thereof
CN106008819A (en) * 2016-07-07 2016-10-12 朗盈科技(北京)有限公司 Production device and method of low-chroma C9 hydrogenated petroleum resin
CN106268824A (en) * 2016-08-08 2017-01-04 农玉金 A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof
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CN107349917A (en) * 2017-07-20 2017-11-17 常熟联邦化工股份有限公司 Highly dissoluble aromatic solvent decolorizing adsorbent and preparation method thereof
CN111019019A (en) * 2018-10-09 2020-04-17 南京雪郎化工科技有限公司 Hydrogenation decoloring method for petroleum resin
CN111333751A (en) * 2020-02-28 2020-06-26 宁波工程学院 Hydrogenation catalysis method of carbon nine resin
CN111333752A (en) * 2020-02-28 2020-06-26 宁波工程学院 Hydrogenation catalysis method of carbon nine resin
CN113880969A (en) * 2021-11-08 2022-01-04 大连理工大学 Method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin
CN114436737A (en) * 2020-10-16 2022-05-06 中国石油化工股份有限公司 Method for comprehensively utilizing C9 fraction generated by ethylene cracking
CN114516926A (en) * 2022-03-11 2022-05-20 广东新华粤石化集团股份公司 Preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin
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CN104628956A (en) * 2013-11-08 2015-05-20 中国石油天然气股份有限公司 Preparation method of C9 petroleum resin
CN105585665A (en) * 2014-10-22 2016-05-18 中国石油化工股份有限公司 A method of preparing hydrogenated petroleum resin through continuous hydrogenation of petroleum resin
CN105585665B (en) * 2014-10-22 2019-06-11 中国石油化工股份有限公司 The method that Petropols continuously hydrogen adding prepares hydrogenated petroleum resin
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CN104877077A (en) * 2015-06-24 2015-09-02 大连理工大学 Method for preparing hydrogenated C9 petroleum resin
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CN106268824A (en) * 2016-08-08 2017-01-04 农玉金 A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof
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CN106832127A (en) * 2017-02-10 2017-06-13 恒河材料科技股份有限公司 A kind of method for orienting the standby hydrogenation C 9 petroleum resin of Hydrogenation
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CN107349917A (en) * 2017-07-20 2017-11-17 常熟联邦化工股份有限公司 Highly dissoluble aromatic solvent decolorizing adsorbent and preparation method thereof
CN111019019A (en) * 2018-10-09 2020-04-17 南京雪郎化工科技有限公司 Hydrogenation decoloring method for petroleum resin
US11613675B2 (en) 2019-01-31 2023-03-28 Synthomer Adhesive Technologies Llc Packaging adhesives comprising low volatile tackifier compositions
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CN111333751A (en) * 2020-02-28 2020-06-26 宁波工程学院 Hydrogenation catalysis method of carbon nine resin
WO2021169016A1 (en) * 2020-02-28 2021-09-02 宁波工程学院 Hydrogenation catalysis method for c9 resin
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CN111333752B (en) * 2020-02-28 2021-06-08 宁波工程学院 Hydrogenation catalysis method of carbon nine resin
CN111333752A (en) * 2020-02-28 2020-06-26 宁波工程学院 Hydrogenation catalysis method of carbon nine resin
CN114436737A (en) * 2020-10-16 2022-05-06 中国石油化工股份有限公司 Method for comprehensively utilizing C9 fraction generated by ethylene cracking
CN113880969A (en) * 2021-11-08 2022-01-04 大连理工大学 Method for preparing hydrogenated petroleum resin by hydrogenation of cold-polymerized petroleum resin
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